Best twitch people I follow:
http://www.twitch.tv/witwixSuper funny and engaging dude who speedruns 'I Wanna Be the Boshy' and recently expanding to playing other things as well. Has a super dry wit and has great chat interaction. He's been rising in popularity over the last year and last AGDQ was pretty huge and increased his footprint on Twitch by a significant margin. Stream schedule tends to be more in the late night area but shifts around a lot.
http://www.twitch.tv/bananasaurus_rexFormally known for his WR Spelunky runs, but lately has been LPing older games he missed out on his childhood. Sometimes he'll speedrun a game or two, recently Wings of Vi. Also a pretty funny dude. Great voice, and it's really fun to watch him get salty at games. Stream schedule also tends to be in the late night but also shifts around a lot.
http://www.twitch.tv/elajjazSwedish dude who speedruns Dark Souls primarily but has also run Demon's Souls, Dark Souls 2, and Shadow of the Colossus as well occasionally. He's not as witty as others, but he's a fun dude to watch. Stream schedule is during the day the majority of the time, anywhere from ~10am - ~6pm EST.
http://www.twitch.tv/zoastySpeedruns Super Metroid. Doesn't stream all that often unfortunately but I've been a fan and been watching well over a year now. Stream schedule usually is in the afternoon due to having a full-time job. Generally after 5pm EST
http://www.twitch.tv/richard_hammerFormerly Dick Hammer. He primarily plays Binding of Isaac but dabbles in other games as well. Recently Darkest Dungeon. He's done a lot of funny interesting stuff in his life, like going to jail for selling crack when he was young. He's super open about telling stories from his life and he's great at telling them. Stream schedule focuses on late-night 12am EST onward.