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Sure it would work... terribly. You've specified no objective though, so how are we to evaluate the question?
TEGs are like 5% efficient if you've set them up correctly (lots of heating and cooling surface area on both sides). AC is generally over 100% efficient by comparison.
I once bought a peltier cooler so I could experiment with overclocking my CPU. Even with a triple fan massive heatsink, it couldn't seem to dissipate heat fast enough to shed the minor amount of heat generated by the CPU plus the massive amount generated by the peltier. That, and there were concerns about condensation (you want water dripping from your headliner?).
So, you could mount peltiers to the roof, but it wouldn't have enough surface area to even achieve 5% efficiency, and you'd be rained on by condensation. The roof would turn into a giant frying pan before it was able to cool the cabin reasonably.
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