A molybdenum-mediated reductive ortho-alkylation of nitroarenes with alcohols for the synthesis of ortho-alkylated anilines has been developed. Using Mo(CO)6 as both the reductant and the catalyst, a range of ortho-alkyl-substituted anilines were prepared from nitroarenes and alcohols. Preliminary mechanistic studies indicate that nitroarenes were reduced by Mo(CO)6 to aniline in the presence of H2O, while an oxidized Mo species catalyzed the alkylation portion of this reaction.