The influence of a polymer matrix containing different amounts of 4-N-pyrrolidinopyridine and pyridylmaleimide units in the main chain on the catalytic properties of rhodium catalysts fixed in the matrix in the olefin hydroformylation reaction was studied. By Fourier transform IR and X-ray photoelectron spectroscopy techniques, it was shown that the complexation of rhodium with polymeric ligands occurs via nitrogen atoms of pyridine rings. It was found that the polymeric support in the case of copolymers with pyrrolidinopyridine groups acts as a cocatalyst and allows the activity of a rhodium complex in the hydroformylation of poorly reactive olefins such as 2-butenes and isobutene, to be significantly enhanced. Moreover, there is an increase in the yield of normal-chain aldehydes in the hydroformylation of 1-hexene and 2-butenes in the case of copolymers containing more basic nitrogen, since coordination to rhodium leads to the formation of a greater number of intermolecular crosslinks, providing steric control at the substrate isomerization step.