Veronica — Gunn had a romance with this girl prior to becoming a full-time member of Angel Investigations. She appears briefly in the Season Two episode "First Impressions", in which her non-fatal injury at the hands of a vampire brings back painful memories and feeling of guilt about Alonna.

Winifred Burkle — Gunn and Fred fall in love and continued a strong relationship throughout much of Seasons Three and Four. However, an incident in which he murdered a human being in order to protect Fred's innocence led to the end of their close relationship. Nevertheless, he retains strong feelings of friendship for her and is devastated by her death, for which he is partially responsible. Unlike the other characters, who usually referred to Gunn by his surname, Fred always called him Charles and continued to do so following their break-up.

Gwen Raiden — Gunn and Gwen flirt and have sex in the episode "Players" in which Gwen gains the ability to touch people without harming them.