A novel and convenient approach to the synthesis of various tertiary phosphine oxides via nickel-catalyzed cross-coupling of (het)aromatic tosylates with secondary phosphine oxides is developed. The reaction employs cheap nickel as the catalyst, 1-(2-(di-tert-butylphosphanyl)phenyl)-4-methoxypiperidine (L3) as the ligand, and pyridine as the base. This reaction produces the corresponding (het)aromatic phosphorus compounds in good to high yields. Moreover, four new tertiary phosphine oxides are reported in this process.