For the first time, palladium complexes with salicylaldehyde thiosemicarbazones were applied as catalyst precursors to the Suzuki–Miyaura reaction. These air and moisture stable phosphine-free systems efficiently catalyze the cross-coupling of aryl bromides and chlorides (from electron rich to electron poor) with phenylboronic acid in DMF/H 2 O at 100°C for 24h, using Na 2 CO 3 as base, without addition of free ligand or any promoting additive, and under aerobic conditions no significant homocoupling of phenylboronic acid to unsubstituted biphenyl was observed.