Substituted vanadium carbonylcompounds with η2-bonded acyl ligands (η2-RCO)V(CO)3 ( = ditertiary phosphines or arsines: dppe, dppp, dppm, diars, arphos, dpase) have been prepared by photochemical reaction of [V(CO)4] with various substituted benzoyl chlorides and cyclopropanylcarbonyl chloride.