Following the suspension from her position at William McKinley High School, cheer-leading coach Sue Sylvester (Jane Lynch) blackmails Principal Figgins (Iqbal Theba), slipping him a date rape drug and taking an incriminating photograph of them in a compromising position. He allows her to return to work at the school, where she immediately returns to plotting to bring down New Directions. Finn Hudson (Cory Monteith) and Rachel Berry (Lea Michele) are now dating, although Finn still is not over his ex-girlfriend Quinn Fabray (Dianna Agron). He expresses his feelings through a performance of the Doors' "Hello, I Love You" as part of the week assignment of performing songs with the word "Hello" in the title.
Sue enlists cheerleaders Santana Lopez (Naya Rivera) and Brittany Pierce (Heather Morris) to seduce Finn. He breaks up with Rachel, who angrily sings "Gives You Hell" in retaliation, and goes on a date with both Brittany and Santana, but comes to the realization that he does want to be with Rachel. In the interim, Rachel meets Jesse St. James (Jonathan Groff), the lead singer of New Directions' rival glee club Vocal Adrenaline, at a local music library. The two perform an impromptu duet of Lionel Richie's "Hello", and Rachel becomes enamoured with him. Eventually, the New Directions members learn about the blossoming relationship and conclude that Jesse is using Rachel, and threaten to expel her from the club unless she breaks up with him. Rachel asks Jesse to keep their relationship a secret and turns Finn down when he asks her to get back together with him.
Glee club director Will Schuester (Matthew Morrison) begins dating guidance counselor Emma Pillsbury (Jayma Mays). Emma suffers from mysophobia and is uncomfortable kissing Will. She admits that she is still a virgin, and requests that they take their relationship slowly. While dancing, Will sings Neil Diamond's "Hello Again" to her. When Emma is preparing dinner for Will several nights later, his ex-wife Terri Schuester (Jessalyn Gilsig) arrives at the apartment, and tells Emma that she and Will danced to "Hello Again" at their prom in 1993, leaving Emma distressed.
On a visit to Carmel High School, Will meets Shelby Corcoran (Idina Menzel), the coach of Vocal Adrenaline, while she has the club perform a rendition of "Highway to Hell". She flirts with Will and eventually seduces him. However, Will is unable to continue and tells her about his relationship problems. Shelby suggests that as Will had been with Terri since he was 15 and has immediately moved on to a new relationship, he ought to take some time out for himself. She later observes as Jesse and Rachel kiss, and exchanges knowing looks with Jesse.