DogeCoin was the first coin that had random block rewards, and BlackCoin the first PoW/PoS hybrid.
A bit inaccurate
.First random block reward coin was Junkcoin.
First PoW/PoS hybrid was Novacoin
Edit:
First PoW/PoS hybrid was Peercoin for SHA and Novacoin for script.
LOL. I just got that from the BlackCoin website, since it says it "is the first PoW/PoS hybrid coin to fully reach the purely PoS stage"