Performers: Gunnar (Sam Palladio) and Scarlett (Clare Bowen) Rayna and Juliette may have been the established country stars when Nashville launched, but by far the most memorable performance of the pilot was delivered by these two struggling singer-songwriters. Scarlett's deep, haunting voice particularly seems like it should be coming from the mouth of a woman much older and with much more life experience — which probably explains why the "Pope of Nashville," Watty White, called Rayna from the Bluebird and held the phone up for her to hear the future of country music for herself.

Performers: Rayna James (Connie Britton) Disgusted with her husband Teddy and father Lamar for pulling a dirty trick during Teddy's campaign for mayor, Rayna decides to drown her sorrows at the recording studio with a tumbler full of whiskey. The result? A (somewhat drunken) performance that record producer Liam calls "electric" and that captures exactly the new sound Rayna's going for. Also, cue the first moment of sexual tension between Liam and Rayna!

Performers: Rayna (Connie Britton) and Juliette (Hayden Hayden Panettiere) They may be nothing more than rivals off the stage, but when Rayna and Juliette team up for this performance in Season 1, there's nothing but sweet harmony between them. And in writing the kiss-off together, Rayna and Juliette realize that they may have more in common than they thought. Don't underestimate these two! It's performances like this one that make us wish the two songstresses could put their differences behind them once and for all.

Performers: Maddie (Lennon Stella) and Daphne (Maisy Stella) We already knew these two could sing, but when Rayna lets her daughters share the spotlight with this Lumineers track during sound-check, viewers realized these sisters were stars. Although no one knew it at the time, it's also one of the first times Deacon got to see that Maddie is an apple that didn't fall far from his talented tree.

Performers: Juliette (Hayden Hayden Panettiere) and Deacon (Charles Esten) Prior to this scene, we thought Juliette was a brat with a good voice and a strong writing team. But the moment we watched her and Deacon write together, it became apparent the girl had some serious talent — and some serious struggles. Besides delivering one of the show's catchiest tunes yet, this scene also showed the great chemistry this duo would develop.

Performers: Gunnar (Sam Palladio) and Scarlett (Clare Bowen) No one can say they didn't see the relationship between Gunnar and Scarlett coming after this touching performance from the collaborators-turned-lovers in Season 1. Watch the sparks fly as they (and Scarlett's boyfriend at the time, Avery) realize there might be more to their songwriting partnership than just musical harmony. It's no coincidence that "I Will Fall" is also the song that causes Juliette to snap to attention when the duo performs it at Deacon's birthday party later in the season.

Performers: Rayna (Connie Britton) and Deacon (Charles Esten) Thanks to those telling flashbacks in the Season 2 premiere, fans know all too well the long history between former lovers Rayna and Deacon. But back when the duo performed this duet at the Bluebird Café in the series' second episode, this tune's stirring lyrics helped catch fans up on just what went down way back when, and the love these two still share. Lyrics like "I know why you're lonely. It's time you knew it, too. … No one will ever love you ... like I do" might seem a bit cruel, but it's all too true.

Performer: Juliette (Hayden Panetierre) The usually over-produced Juliette ends Season 1 on a vulnerable note as she strips down the theatrics for this acoustic number at the Bluebird. Dedicating the song to her recently deceased mother, you can almost hear the tears in Juliette's voice as she both mourns her loss, but the song is also a bit of an anthem, as Juliette vows to find the "one way up when you're at zero." The touching ballad also underscores Gunnar's proposal to Scarlett and Rayna and Deacon's heartbreaking fight which ends with Season 1's cliff-hanger car crash.

Performer: Rayna (Connie Britton) Although Nashville has proven the title of this song over and over, this performance is actually more of a celebration than a pity party. Forced on-stage during a benefit concert, Rayna takes the mic despite being unsure if her voice has returned following her car accident. When she makes it through the first few lines, Rayna is overcome by emotion that only grows stronger as the audience sings the words for her. Confident, she finally belts out the big chorus, proving the queen of country music is here to stay.

Performer: Gunnar (Sam Palladio) and Will (Chris Carmack) This boot-stomping electric ditty provided a confidence boost for Gunnar as he struggled in his relationship with Scarlett after the death of Gunnar's brother. Energized by performing with Will, Gunnar grabs people's attention by embracing the outlaw spirit of his dead brother's lyrics. The performance earns Gunnar a shot at cutting a demo, but unfortunately, Gunnar later has second thoughts about stealing his brother's material. If they all turned out like this song, maybe he should keep it up!

Performer: Will (Chris Carmack) This catchy, high-energy track, is the perfect single to launch Will's new career at Edgehill records. And that's exactly why he performs it in front of his new bosses. Unfortunately, he didn't ask permission from Gunnar, the song's author. Although Will insists the song will make Gunnar lots of money, Gunnar refuses to let him record it, especially after Will belittles Gunnar by calling him a songwriter rather than a performer.

Performers: Deacon (Charles Esten) and Scarlett (Clare Bowen) Sometimes the spotlight of stardom can be rough, especially on a newcomer like Scarlett. After a particularly bad night on her first red carpet, she performed this dark tune with Deacon, who was going through his own struggles after his car accident. This song not only marked a rare performance between uncle and niece, but also one of Deacon's first musical performances after learning about the extensive damage done to his hand. It may not be an electric guitar, but his piano-playing skills aren't too shabby.

Performers: Maddie (Lennon Stella) and Daphne (Maisy Stella) We could listen to these harmonizing sisters sing all day, but it was especially meaningful to watch Maddie find comfort and meaning in song her biological dad had written years before. (Like Rayna, who was listening outside their door, we were a little misty too.) Now, when will we get to hear Maddie and Deacon sing this tune together?