The first implementation of a molybdenum complex with an easily accessible bis-N-heterocyclic carbene ligand to catalyze β-alkylation of secondary alcohols via borrowing-hydrogen (BH) strategy using alcohols as alkylating agents is reported. Remarkably high activity, excellent selectivity, and broad substrate scope compatibility with advantages of catalyst usage low to 0.5 mol%, a catalytic amount of NaOH as the base, and H2 O as the by-product are demonstrated in this green and step-economical protocol. Mechanistic studies indicate a plausible outer-sphere mechanism in which the alcohol dehydrogenation is the rate-determining step.