I got this list from Juan F. Lara's Pepper Ann Episode Guide, which is no longer up. I also added a couple one-time voices. If anyone knows of any other particular special voices (i.e. a character that appeared is just one episode) that aren't listed here, please e-mail them to me at serene_universe@yahoo.com. Also, if I have a listing that is incorrect (I placed a ? by those I'm unsure of), please e-mail me and let me know. Thanks to Rayden for this idea!
| Voice | Character(s) |
| Kathleen Wilhoite | Pepper Ann Pearson |
| Danny Cooksey | Milo Kamalani |
| Clea Lewis | Nicky Little |
| April Winchell |
Lydia Pearson Lillian Lilly Ms. Abriola Stark Sherie Spleen Milicent the Militant |
| Pamela Segall | Magaret Rose "Moose" Pearson |
| Don Adams | Principal Herbert Hickey |
| Jeff Bennett |
Dieter Lederhosen Shelf McLain Craig Bean "Pink-Eye" Pete Ogilve Nedward Diggety Mrs. Lederhosen Giraffe head ("Megablades of Grass") Bump the Gas Pump ("Quiz Bowl") (?) Emmitt |
| Jenna Van Oy | Trinket St. Blaire |
| Kath Soucie |
Cissy Rooney Gina & Tina Mrs. Little Supermodel Mindy |
| Cree Summer-Francks | Tessa & Vanessa James |
| Luke Perry | Stewart Walldinger |
| Kimmy Robertson | Gwen Mezzrow |
| Susan Tolsky | Aunt Janie Diggety |
| Tino Insana | Uncle JoJo Diggety |
| Maurice LaMarche |
Leo Lilly Chuck Pearson |
| Adam Wylie | Crash |
| Paddi Edwards | Vera |
| Kathy Najimy |
Coach Doogan Margot LaSandre |
| Jim Cummings |
Mr. Roland Carter Mr. Little |
| Don Lake | Mr. Sherman Finky |
| Bebe Neuwirth | Ms. Bronte Bladdar |
| James Avery | Mr. Clapper |
| Ellen Cleghorne | Nurse Oomla |
| Julia Sweeny | Ms. Carlotta Sneed |
| Wallace Langham | Wayne MacCabre |
| Lauren Tom | Alice Kane |
| Candi Milo | Constance Goldman |
| Kenny Blank | Lamarr Abu Dahbi |
| Tara Charendoff | Brenda ("Old Best Friend") |
| Karen Duffy | Sketch |
| Meridith Scot Lynn | Poison |
| Brittany Murphy | Tank |
| Mark Hammil |
Himself ("Complimentary Colors", "Portrait of the Artist as a Young Milo") |
| Evel Knievel | Himself ("Beyond Good and Evel") |