A transition‐metal‐free and regioselective synthesis of a series of 2‐amino‐4‐alkoxypyrimidines is described. The SNAr alkoxylation of 2,4‐dichloropyrimidines regioselectively provided 2‐chloro‐4‐alkoxypyrimidines, which were subsequently subject to the second SNAr amination with cyclic amines in the presence of triethylamine at high temperature to afford 2‐amino‐4‐alkoxypyrimidines in good overall yield.