Catalytic C-N and C-S bond forming reactions of haloarenes with secondary amines and benzenethiols were achieved in water under heterogeneous conditions by the use of immobilized palladium complexes coordinated with the amphiphilic polystyrene-poly(ethylene glycol) resin-supported di(tert-butyl)phosphane ligand to afford aryl(dialkyl)amines and diaryl sulfides in high yield.