N,N,P-Pincer nickel complexes effectively catalyze reaction of alcohols with benzylphosphine oxides to form alkenes in good yields. The protocol suits for a wide scope of substrates and generates only E-configurated alkenes. The method also shows good compatibility of functional groups. Methoxy, methylthio, trifluoromethyl, ketal, fluoro, chloro, bromo, thienyl, and furyl groups are tolerated. The mechanism studies support that the reaction proceeds through catalytic dehydrogenation of alcohols to aldehydes or ketones followed by condensation with benzyldiphenylphosphine oxides in the presence of KOtBu.