I can't speak with authority on his mental state at the time, but I was a participant in the online conversation during which his transition occurred, and I would say that it seemed like a click moment. He had already been grappling with religious issues and attempting to reconcile them in a rational way, and had started to make a headway on the sequences, and in the course of that conversation, he seemed to realize that there were simple and obvious reasons why the approach he had been taking didn't make sense, that the mistakes were correctable, and that by making a generalized effort to recognize and avoid those sort of mistakes, he could make his reasoning more correct.
He already had the relevant information, but the connection was a relatively sudden event.
Edit: wrote this after seeing Raw Power's comment in the recent comments bar without noticing the date of the comment he was responding to. I interpreted it as a question to Raw Power.
To break up the awkward silence at the start of a recent Overcoming Bias meetup, I asked everyone present to tell their rationalist origin story - a key event or fact that played a role in their first beginning to aspire to rationality. This worked surprisingly well (and I would recommend it for future meetups).
I think I've already told enough of my own origin story on Overcoming Bias: how I was digging in my parents' yard as a kid and found a tarnished silver amulet inscribed with Bayes's Theorem, and how I wore it to bed that night and dreamed of a woman in white, holding an ancient leather-bound book called Judgment Under Uncertainty: Heuristics and Biases (eds. D. Kahneman, P. Slovic, and A. Tversky, 1982)... but there's no need to go into that again.
So, seriously... how did you originally go down that road?
Added: For some odd reason, many of the commenters here seem to have had a single experience in common - namely, at some point, encountering Overcoming Bias... But I'm especially interested in what it takes to get the transition started - crossing the first divide. This would be very valuable knowledge if it can be generalized. If that did happen at OB, please try to specify what was the crucial "Aha!" insight (down to the specific post if possible).