A series of arsine‐ and stibine‐ligated Schiff base palladacycles were synthesized by the reaction of μ‐Cl‐bridged Schiff base palladacycles [Pd(C6H4CH]NC6H2R)(μ‐Cl)]2 (R = 2,4,6‐trimethyl or 2,6‐diisopropyl) with AsPh3 or SbPh3. The new arsine‐ and stibine‐ligated palladacycles were fully characterized using 1H NMR, 13C NMR and infrared spectroscopies, high‐resolution mass spectrometry, elemental analysis and single‐crystal X‐ray diffraction. Further exploration of the catalytic application of the palladacycles for Suzuki–Miyaura cross‐coupling reactions of aryl bromides with arylboronic acids was carried out. It was found that the new palladacycles are considerably active for these coupling reactions. Copyright © 2016 John Wiley & Sons, Ltd.