Poly(arylene ether triaryl phosphine oxide)s were synthesized by nucleophilic aromatic substitution reaction of bisphenolates and bis(4,4’-fluorophenyl)phenyl phosphine oxide. Amorphous, transparent, high glass transition temperature materials are produced that are soluble in a number of solvents. The macromolecular aryl phosphine oxide structure was successfully reduced with phenylsilane in chlorobenzene at 110 degrees C to produce the corresponding poly(arylene ether triphenyl phosphine). The model precursor polymer was soluble in toluene and was used as a ligand for the hydroformylation of octene-1. The soluble rhodium species was based upon Rh(acac)(CO)(2). When the two component solutions were combined they produced a heterogeneous catalyst which was reacted with octene-1 and purified synthesis gas in a pressure reactor. Various ratios of polymeric phosphene ligands were investigated and an 8 : 1 ratio produced 95% conversion in 3 h at 120 degrees C. The polymeric catalyst demonstrated improved selectivity of normal to branched aldehydes relative to a control conventional catalyst.