A metal-free oxynitration of acrylamides with commercially available tert-butyl nitrite and easily available air was achieved through a regioselective pathway. A wide range of 1,2-nitro alcohols were thus efficiently synthesized in a novel route under mild conditions. The reaction involves a radical process, allows a highly regioselective strategy toward the formation of new CÀ N and CÀ O bonds in one step.