Air-stable neutral and cationic palladium complexes bearing chiral phosphine-N-heterocyclic carbene ligands with planar chirality only have been prepared in moderate to good yields and characterized by NMR and X-ray diffraction studies. They are shown to catalyze the asymmetric coupling of aryl bromides with arylboronic acids in good yields and moderate enantioselectivities (up to 42% ee) with low catalyst loadings (0.1−0.5 mol %).