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An undersock is a lifesaver, especially on long walks and hikes, when paired with another sock: one pair of snug, thin socks against the skin and another pair of airier socks on top. The main function of the socks is to transfer any chafing between the two layers of socks, rather than directly to the skin. The socks and the two-sock technique need to be paired with shoes that are loose enough to allow the foot to move and the blood to circulate properly through the feet.
In addition to a snug fit, you should prefer breathable materials in your socks. Made by Sockmasters, these underwear are made from merino wool with technical synthetic fibres added for added flexibility and wear resistance. Merino wool is pleasantly soft, highly breathable and moisture wicking. This means that your feet stay dry even on long journeys. Merino wool dries quickly, so you can hang socks that feel damp in the corner of your backpack on a hike. This way they're ventilated and dried fresh again for the next stop.