α-Alkylation of methyldiarylphosphine oxides with (hetero)arylmethyl alcohols was performed under nickel catalysis. Various arylmethyl and heteroarylmethyl alcohols can be used in this transformation. A series of methyldiarylphosphine oxides were alkylated with 30–90% yields. Functional groups on the aromatic rings of methyldiarylphosphine oxides or arylmethyl alcohols including OMe, NMe₂, SMe, CF₃, Cl, and F groups can be tolerated. The conditions are also suitable for the α-alkylation reaction of dialkyl methylphosphonates.