First appearance
By alphabetic order
A – H
- Amy: S01 E03 – Witch
- Angel: S01 E01 – Welcome to the Hellmouth
- Anya: S03 09 – The Wish
- Buffy: S01 E01 – Welcome to the Hellmouth
- Cordelia: S01 E01 – Welcome to the Hellmouth
- Chanterelle / Lily: S02 E07Lie to me
- Ethan Rayne: S02 E06 – Halloween
- Faith Lehane: S03 E03 – Faith, Hope & Trick
- Darla: S01 E01 – Welcome to the Hellmouth
- Drusilla: S02 E03 – School Hard
- Giles: S01 E01 – Welcome to the Hellmouth
- Harmony: S01 E02 – The Harvest
I – Z
- Jenny (Miss Calendar): S01 E08 – I, Robot… You, Jane
- Jonathan: S02 E04 – Inca Mummy Girl
- Joyce (Buffy’s mum): S01 E01 – Welcome to the Hellmouth
- Kendra: S02 E09 – What’s My Line? #1
- The Master
- The Mayor: S03 E05 – Homecoming
- Oz: S02 E04 – Inca Mummy Girl
- Spike: S02 E03 – School Hard
- Wesley Wyndam-Pryce: S03 E14 – Bad Girls
- Willow: S01 E01 – Welcome to the Hellmouth
- Xander: S01 E01 – Welcome to the Hellmouth
By season
First appearance during the 1st episode of the 1st season
- Angel
- Buffy
- Darla (1st scene)
- Cordelia
- Giles
- Joyce
- Willow
- Xander
Season 01
- Amy Madison
- Angel
- Buffy
- Darla
- Cordelia
- Giles
- Harmony
- Jenny
- Joyce
- Kendra
- Oz
- Willow
- Xander
Season 02
- Chanterelle / Lily (season 3)
- Drusilla
- Ethan Rayne
- Jonathan
- Kendra
- Spike
Season 03
- Anya
- Faith
- The Mayor
- Wesley Wyndam-Pryce