AbstractTriphenylphosphine ligand functionality could be readily introduced onto the 2% DVB and 12% DVB cross‐linked polystyrenes. Significant differences in reaction rates and loading capacities were observed in favor of the 2% DVB percentage cross‐linkage. The reaction of iron pentacarbonyl with polymeric ligand gave both monocoordination and biscoordination products. Product distribution analyses indicated that monocoordination was favored for both kind of polymeric ligands. Ratio of biscoordination to monocoordination was higher for the 2% DVB polystyrene ligand than for the 12% DVB polystyrene ligand indicating biscoordination proceeded more easily on the for