That right there is the very essence of a lie: getting someone to beleive what you want them to believe, through deception with words and actions. And since Sense Motive opposes a Bluff, sense motive can discern if there is a lie: if they're trying to get you to beleive something they want you to believe.
In D20 Modern, there's a class that can use Sense Motive as a lie-detector - so most characters can't do that. It was explained in a Bullet Points column.
IMC, you get one Sense Motive per conversation. Sometimes you can see through a lie because you know facts that the bluffer thinks you didn't know, of course.