I see a lot of people are wearing cotton socks. That surprises me. There are a lot of modern non-scratchy blends or synthetics available. Some of the blends/synths are a bit more pricey, so I wouldn't use them every day, but for stuff where I'm away from my vehicle/civilization and there might be "weather," I figure the price is worth it. Don't want cotton on me in cold and wet conditions.

Have you ever tried to dry out a pair of GI socks? I'm not trying to be critical, but that's every GI's lament; GI socks take for freaking ever to dry.

I agree with Jeff that boot fit, break-in, and adjustment is key, and a good pair of insoles makes a huge difference. Perhaps this goes w/o saying, but with new boots, take 'em out enough times that they not only "break in" but also so you get used to what lacing and socks work well.
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Adventures In Stoving