From a 2004 interview with Cathleen Falsani in the Chicago Sun-Times:
Falsani: Do you believe in sin?
Obama: Yes.
Falsani: What is sin?
Obama: Being out of alignment with my values.
Well, at least the question of his religion is settled. It’s not Christianity or Islam.
It’s himself.
via Roger Kimball
(Crossposted at Sister Toldjah)

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I was expecting him to see Killer Bob in the mirror; knowing that he is possessed by a denizen of the Black Lodge would make some sense of the weird crap that has been going on since he assumed the office. It sometimes certainly feels like we are living in an episode of Twin Peaks.
Without knowing the context, it sounds to me like he means he’s sinning when he is out of alignment with his values.
No mention of God’s values, though, so I guess we just have to presume that they are the same.