Two percent divinylbenzene (DVB)-crosslinked polystyrene was prepared and functionalized to obtain its aldehyde analog. Amino porphyrins were anchored on this polymer support by Schiff base condensation. The anchoring positions were adjusted so as to obtain ortho-, meta-, and para-isomeric systems. The polymer-bound free-base porphyrins were metallated to obtain the corresponding Cu(II) and Ag(II) complexes by treating them with the corresponding metal salt solutions. The products were characterized chemically and spectroscopically. Electronic and ESR spectral analysis shows the microenvironmental participation of the polymer network on the electronic levels of the porphyrin system. The extents of steric and electronic participation were evaluated and are presented.