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The only times I can think of that Vader might have seen the droids:
1. On the first Death Star, after he kills Obi-Wan, the droids are with Luke, Leia, Han and Chewie as they run aboard the Millenium Falcon. (Although, it's possible that they might have gotten aboard the Falcon while Vader was preoccupied with "what happened to Obi-Wan?" and he didn't see them.)
2. As he pursues Luke down the trench, R2D2 is flying with Luke. (Many astromech droids look alike though, and it's understandable if he didn't recognize R2.)
3. However, the most obvious one: As Han is being carbon-frozen on Bespin, Chewie is carrying Threepio on his back. Threepio won't shut up during this scene, and in fact Vader even reacts to one of his comments, so he KNEW he was there.
-Mikey
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