AbstractA metal and catalyst‐free, environmentally friendly synthesis of hindered dialkyl ether derivatives has been established via the nucleophilic alkoxylation of alcohols and α‐halohydroxamates. The reactions of a variety of primary and secondary alcohols with azaoxyallyl cations generated in situ from α‐halohydroxamates afforded a wide range of hindered dialkyl ether derivatives in good yields. Moreover, methods for the synthesis of α‐alkoxyhydroxamic acids, α‐alkoxy amides, and α‐hydroxy amides from α‐alkoxy hydroxamates were established.