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I have found, when having to do a lot of hiking in the high desert while living in a tent for weeks at a time (for work), gold bond powder works pretty well if the chafing has already occurred. Ultimately, non-bunching quick drying underwear (already mentioned) is the best defense against the development of chafing. But for me, when in hot climates, the drying action of gold bond powder is much more pleasant than greasy options. Scorpion crotch is no fun.
If you already have a rash, Desitin.