Our Lady of Perpetual Sorrow is a private Roman Catholic religious teaching school located in the city of Boston. Maddie was taken to this school by her parents. At the school, she met some new friends named Corrie, Mary-Margaret, and Leslie. They studied together and bonded together. Later London Tipton was tranferred to this school because she was getting kicked out of all the other schools. Besides teaching the religious Roman Catholic beliefs, the schools also has gym, cafeteria, volunteer work and more. The teachers are nuns or sisters who are very active within the Roman Catholic religion.
- Sister Dominick (played by Marianne Muellerleile) - London and Maddie's teacher who works at Our Lady of Perpetual Sorrow as a nun/teacher. She seems to favor London over Maddie, even though Maddie is the hard working student. Sister Dominick is strict and very religious. Her cell phone’s ring tone is, "Hallelujah Chorus," to which she answers, "Bless you for calling." It has been revealed that she and the other nuns are infatuated with wrestling, and that Sister Dominick herself has a 'mean body slam' in the episode What's The Hey?.
- Sister Rose (played by Mindy Sterling) - The gym teacher of the school. She is a Catholic nun or sister who participates in athletic events in the school. She only appears in one episode, when London and Maddie are chosen onto the same volleyball team.
- Maddie Fitzpatrick (played by Ashley Tisdale) - She's a great student, she says about she ever ate all the things to the school gave to her, she ever obeyed and she never be punish, except for the blame of London in Forever Plaid.
- London Tipton (played by Brenda Song) - She's a bad student, but the Sister Dominick thinks the oposite, because she ever bring the credit, when she made to punish her and Maddie, but she said to all the blame is for her, and the Sister thinks she is honest, also, when she, Mary-Margaret, Corrie and Maddie were painting an appartament, all the credit (also paparazzis) was for her.
- Mary-Margaret (played by Monique Coleman) - Mary-Margaret is Maddie's friend from school. Not much is known about her, except she's smart and only likes London for her money and possessions. When she first met London, she initially seemed to be annoyed, as shown in A Prom Story, but in Forever Plaid and Not So Suite 16, she appeared to be London's friend. Mary-Margaret is on Maddie's volleyball team along with London and Leslie, as shown in Volley Dad.
- Corrie (played by Vanessa Hudgens) - Corrie is a schoolmate of Maddie, Mary Margaret, and her idol London at Our Lady of Perpetual Sorrow. She is very perky, obsessed with London, and not very bright.