Selenoether ligands, 2,2′-methylenebis(selanediyl)bis(2,1-phenylene)dimethanol ( 5), (2,2′-(ethane-1,2-diylbis(selanediyl))bis(2,1-phenylene))dimethanol ( 6) and (2-(benzylselanyl)phenyl)methanol ( 7) have been synthesized by reducing di- o-formylphenyl diselenide and reacting the in situ generated selenolate with dibromomethane, 1,2-dibromoethane and benzyl chloride, respectively. The ligands, bis(2-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)phenylselanyl)methane ( 8) and 1,2-bis(2-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)phenylselanyl)ethane ( 9) have been synthesized similarly from bis[2-(4,4-dimethyl-2-oxazolinyl)phenyl] diselenide using electrophiles dibromomethane and 1,2-dibromoethane, respectively. Activity of ligands 5–9 along with 2-(2-(benzylselanyl)phenyl)-4,4-dimethyl-4,5-dihydrooxazole ( 10) and 1-(2-(benzylselanyl)phenyl)-N,N-dimethylmethanamine ( 11) were examined for the Heck reaction of aryl halides with olefins. Bidentate Se,N ligand 11 was found to be the best one in the series and constitutes an efficient phosphine-free catalytic system with PdCl 2. The catalytic system showed moderate activity for the coupling of activated aryl chlorides in the presence of tetra- n-butyl ammonium bromide (TBAB). Complexes [ 10-PdCl 2] ( 12) and [ 11-PdCl 2] ( 13) have shown marginally better activity in comparison to the in situ generated catalysts from PdCl 2 and 10 and 11, respectively in the coupling of 4-bromoacetophenone with n-butylacrylate. Ligand 9 and complex 13 have been characterized by single crystal X-ray diffraction analysis.