The development of highly efficient and stable Rh-based heterogeneous catalysts for hydroformylation of heavier olefins is of both high fundamental and industrial interest, yet there still remains a tremendous challenge. In this contribution, a series of porous organic polymers bearing various concentrations of triphenylphosphine (PPh3()) moieties, a ligand of industrial choice, was synthesized and their performance in the hydroformylation of styrene, 1-ocetene, and 2-ocetene were investigated after metalation with Rh species. Both concentration of PPh3 moieties and pore structure of the polymers were found to influence the catalytic performance. The polymerbased rhodium catalysts demonstrated an increase in catalytic activity, selectivity, and stability when the concentration of PPh3 was increased and the porous polymer constructed by the functional PPh3 monomer (POL-PPh3) was found to be optimal among all the solid ligands tested. We anticipate these results will form the basis for a constructive perspective in the development of high performance heterogeneous Rh-based hydroformylation catalysts. Moreover, our observations indicate the considerable potential of porous organic polymers (POPs) as a new generation of heterogeneous catalytic platforms that may prove effective when targeting important but highly challenging reactions.