SEASON 4
Ep 10: Heaven and Hell
Dean Where's your boss?
Uriel: He's not here. See, he has this weakness - he likes you
Episode 15: Death Takes a Holiday
Castiel: To everything there is a season
Dean: You made an exception for me
Castiel: You're different.
Episode 16: On the Head of a Pin
Dean: Since when does Uriel put a leash on you?
Castiel: My superiors have begun to question my sympathies
Dean: Your sympathies?
Castiel: I was getting too close to the humans in my charge - you. They feel I have begun to express emotions, the doorways to doubt. This can impair my judgement.
Castiel: For what its worth, I would give anything not to have you do this.
SEASON 5
Episode 2
Castiel: I killed two angels this week. Those are my brothers. I'm hunted, I rebelled, and I did it - all of it - for you. And you failed.
Episode 14
Dean (on the phone): Cas. It's Dean. Yeah, room 31c, basement level, St James Medical Centre.
Cas (standing in front of Dean, on the phone): I'm there now.
Dean: Yeah I get that.
Cas: I'm gonna hang up now"
Dean: Right
Episode 18: Point of no return
Castiel: May be they're desperate. May be they wrongly assumed Dean would be brave enough to withstand them.
Dean: You know what, blow me Cas.
Dean: Woah Cas, not for nothing but the last person that looked at me like that - I got laid.
Castiel: I rebelled for this? So you could surrender to them? I gave everything for you and this is what you give to me?
OFFICIAL TIE-IN NOVELS
War of the Sons by Rebecca Dessertine and David Reed
Page 41 - " 'He's [Castiel's] our friend, but he's still an angel. He hasn't always been honest with us before'. Sam knew that was hard for his brother to hear - Dean had been growing closer and closer to Cass since the angel had rebelled against heaven."
Page 322 (Cas, answering his phone) - "Dean, your absence has been...concerning me"
Page 325 - "Sam and Dean recounted their journey to Castiel over burgers. Sam noticed that Dean left out a lot of details, most of them concerning Julia".
(Dean had slept with Julia, a fellow hunter, and had started to get emotionally involved before returning. Why would he specifically try to avoid telling Cass about it?)
Even some of the writers ship them!