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Austin first coined the phrase after he beat Jake 'The Snake' Roberts (who was in a religious gimmick) in the final of the King of the Ring. This is a paraphrase of what he said, but basically after the match he said:
"[Roberts, you quote John 3:16 at us.] Well, Austin 3:16 says I just kicked your ass!"
That last bit's right, I think.
Anyway, the fans caught onto it, and a phenomenon was born.