I was changing the pads on my *ahem* 2003 chevy venture *ahem* VW and when I compressed the caliper piston back in (bleeder open) I noticed that there was brake fluid in the boot that protects the piston. Is this a sure sign that the caliper needs to be replaced?
I just puked in my mouth

.......a mini van, hehe. Ok I'll shut up now.
Is the boot torn at all? If it is I'd suspect road salt got in there and put some corrosion on stuff. Sittin' here thinkin' about it, that would only happen it the piston seal is in a groove and the caliper housing but most likely the seal is in the piston. Not sure then but I'd try rebuilding it before buying a new one.........if you can even get a rebuild kit, after all it isn't a volkwagen

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If you are sure the fluid didn't slop down from the bleeder I would replace it.. As rabbitman suggested, probably some rust got in there an buggered the seal.. GM's steel quality was rather lack luster in that era.. (I've replaced a lot of calipers and rotors on those things)... IIRC those calipers are pretty inexpensive and most come with a new mounting bracket so that you don't have to deal with cleaning and greasing the slider pins (or trying to get them loose after they rust tight).
gm likes aluminum calipers with plastic pistons too... ive seen plastic pistons crack.. and scrape aluminum and make leak..
I didn't want to get into a rant on GM aluminum calipers... At least most of the minivans got steel calipers.. I think they get them from Prothe....
i think venture is aluminum... why i mentioned it.. and yes they are JUNK...
Might be a brake system option.. I've seen aluminum on the Montannas and Uplander but so far not on the Venture
They looked to be steel. The boot seemed to be fine. I think I'll just go to the wrecker, lots of them there
Most of the time I can just pull calipers apart, clean them up and put them back together (not familiar with the calipers you are working on at all)
Might just be a piece of crud interupted the seal.
No petroleum based products can be used to clean them, the seals will swell.
I put silicone dielctric compound under the boots to help luibricate and hold out moisture.
You should check the price for new calipers, you might be surprised how cheap they are for some cars.