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While prayer is used by those of religious faith, it is also used as a means of communication between humans, angels, and God. Nephilim can also receive prayer. Long before they knew of the existence of angel, Sam prayed everyday.

4.18 The Monster at the End of This Book

Dean prays for Castiel's help when he is trying to stop Sam from meeting with Lilith.

5.18 Point of No Return

Looking to give himself to Michael as a vessel, Dean finds a preacher on the street and asks him to pray to the angels and to them them here is there. Castiel hears this prayer and arrives, beating Dean in anger before taking him back to Bobby's.

7.01 Meet the New Boss

Castiel appears in response to Sam's prayer, when they want to try and get him to return all the souls to purgatory.

9.01 I Think I'm Gonna Like It Here

Dean prayers for any angel to help him, and many of the recent fallen angels answer his call, including Gadreel pretending to be Ezekiel.

13.23 Let The Good Times Roll

When Apocalypse World Michael attacks Sam and Dean in the bunker, Sam prays to Jack for help, who hears his prayer and saves them from Michael.