Abstract The first investigation of air- and moisture-stable diaminophosphine oxides as preligands in the Ni-catalyzed Suzuki cross-coupling reactions of aryl chlorides with arylboronic acids has been reported. The results show that under the optimized reaction conditions, the new catalytic system with a Ni(II) σ-aryl complex as precatalyst and a diaminophosphine oxide as preligand tolerates a variety of functional groups and is efficient for both electron-rich and electron-deficient aryl chlorides, though it shows higher efficiency for activated arylboronic acids than deactivated ones. Steric effects were observed for both aryl chlorides and arylboronic acids.