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Many times I see a friend spectating a match, and I wonder - "are some of the people I know also playing this match?" I don't add all of my "friends of friends", but I (sorta) know them, but maybe not enough to add them/play alone with them.
So, sometimes it's fun to spectate a game a friend is already spectating, since you (both spectators) can talk to each other while watching. However, if I spectate the same game, only to find that I don't know ANYONE in the game being spectated, I have to wait until the game is finished loading before I can quit out of it. (yes, another option is to ask "who are the 5 players you are spectating?" but that could be slightly obnoxious.)
If we could see the player list (both teams) of who is in a current match being spectated in a little pop-up dialog box or something, it would be nice, since you could know whether or not you know enough of the people in the game to even care enough to spectate at all.
(This could actually apply to "In game" as well - i.e "View full player list")
Attached is an edited screenshot to show what I mean: