In Comics
Daredevil #1 (April, 1964)
Web of Spider-Man #18 - The Longest Road
Relatives
Mary MacPherran (Titania) (wife); Jerry Sledge (son); Rockwell "Rocky" Davis (Hi-Llite) (cousin)
Carl Brock (father, estranged), Janine Brock (mother, deceased), Mary Brock (sister), Ann Weying (ex-wife, deceased), Symbiotes relatives: Toxin Symbiote (current symbiote, former grandson), Venom Symbiote (former symbiote, grandfather, former brother), Agony, Phage, Riot, Lasher (uncles, former sons), Scorn (sister, former niece), Carnage (father, former son), Scream (aunt, former daughter, deceased), Hybrid (uncle, former son, deceased)