From their first appearance in More Fun Comics #73 (November 1941):


And from Who's Who: The Definitive Directory of the DC Universe Vol. IX (November 1985):

as well as Who's Who: The Definitive Directory of the DC Universe Vol. XXI (November 1986):


NOTE: Both of those issues of Who's Who had "More Fun Comics #73" as the first appearances for the Golden Age versions of Green Arrow and Speedy, as well as separate entries for the then "current" (Silver Age +) Green Arrow and Speedy that listed Adventure Comics #250 (July 1958) as the first appearances for those entries. Adventure Comics #250 appears to be the first of Jack Kirby's run on the characters.