A new catalytic system for β-alkylation of secondary alcohols has been developed. In the presence of [Cp* IrCl2] 2 (Cp*= pentamethylcyclopentadienyl) catalyst and base, the reactions of various secondary alcohols with primary alcohols give β-alkylated higher alcohols in good to excellent yields without any hydrogen acceptor or hydrogen donor. This reaction proceeds via successive hydrogen-transfer reactions and aldol condensation.