The palladium on carbon (Pd/C)‐catalyzed direct methoxylation of the benzylic positions of linear benzyl and cyclicether substrates proceeded in the presence of i‐Pr2NEt under an oxygen atmosphere to give the corresponding mixed acetals. Cyclic acetal derivatives could also be converted into orthoesters. The present direct methoxylation via a carbon‐hydrogen (C−H) functionalization can be accomplished