Of all the study group members, Annie is the most tolerant and patient when it comes to Pierce. Pierce is often nicer to Annie than he is to anyone else in the group, he appreciates her kindness and tries to reciprocate it. However, he still manages to unintentionally offend her at times with his racist viewpoints and churlish behavior. Despite this, Annie will most often come to Pierce's defense whenever he offends the group. It's because she is unwilling to break up the close circle of friends they have which she considers her family. A few times she had to side with the group when he went to far. A falling out towards the end of their sophomore year together at Greendale resulted in Pierce leaving the study group. However, Annie is genuinely pleased when Pierce decides to return to the group in the following semester. Pierce is portrayed by Chevy Chase and Annie is portrayed Alison Brie. Their first appearance was in the Season One episode Pilot.
|“||You listen up, Pierce! I'm gonna tell you what my mother told me when I wanted to quit cheerleading. 'You're not very pretty, you have no boobs, and you can't do a basket toss to save your life.' But you made a commitment. So pick up your pompoms, Pierce, stuff your bra, and get ready for the team bus to forget you at a Taco Bell, because life is tough. But we soldier on, and that's just the way it goes.||”|
–Annie, "Advanced Criminal Law"
Pierce offers to help write the new school anthem for Annie when she is the chairperson for the committee to come up with the new school song. Annie helps him when he has writer's block and he made a dedication to her in a song that he "wrote". At Annie's "Dias De Los Muertos Party" Pierce, while under the hallucinogenic influence of Star-Burns drugs, gives Annie a creepy back massage. During the school's Valentines Day week celebration, Pierce and Troy are humiliated by Ben Chang and Annie and Shirley team up to get revenge for their friends. At the end of the school year, Pierce and the rest of the study group say their goodbyes to Annie who was leaving for the summer to go with her boyfriend Vaughn to Delaware. He tries to hug her but she instead shakes his hand.
|“|| Annie, I know you're being strong for me. I give you permission to weep.
I'm crying on the inside.
–Pierce and Annie, "Intermediate Documentary Filmmaking"
At the start of the 2010 Fall semester at Greendale, Pierce and Annie reunite with the other study group members in the study room. Messy relationship problems Annie and Pierce had with other people nearly tears apart the study group. Afterwards, Annie notices that Pierce is acting out and hanging out with a group of elderly students who are a bad influence on him. On Halloween, Pierce gets sick during a party Dean Pelton is throwing. Annie, along with Dr. Rich Stephenson, discover that the taco meat served at the festivities has caused a viral outbreak with Pierce being the latest victim. Pierce's misfortune continues when he breaks both legs using a Trampoline and ends up in a wheelchair for a time. When the group searches for Annie's pen, things get heated as accusations start flying concerning who is to blame. Pierce attempts to join in when things spiral out of control after Jeff and Annie start stripping in a convoluted attempt to prove their innocence. On Christmas, Annie, Pierce and the rest of the group participate in a therapy session with Abed. Later, Annie stages an anti-drug play for middle schoolers with Pierce and the study group. When Pierce provides rent money for Annie's apartment, he guilts her into letting him have a bigger part in the play. Afterwards, Annie becomes concerned that Pierce is addicted to his pain medication fir his recent injury and tries to get the group to stage an intervention. When Pierce overdoses, he uses his hospital stay as an opportunity to play a prank on the group. He pretends he is dying and hands out bequeathals. Annie receives a diamond tiara but she returns it believing it to be Pierces way of testing her resolve. He privately admits there were no strings attached to the gift and that he gave her the tiara because she is his favorite in the group.