A vinyl monomer containing the pendant tetraphenylporphyrin (TPP) group, 4-vinyltetraphenylporphyrin (VTPP), was synthesized. A homopolymer (PVTPP) which is insoluble in water, and three water-soluble polymers were obtained by radical polymerization. The water-soluble polymers are two anionic polymers (PVPTSPP and PVTPP-StSO3) and a cationic polymer (PVTPP-VPyM). PVPTSPP has sulfonic acid groups in a TPP group and very high charge density. PVTPP-StSO3 was obtained by copolymerization of VTPP and sodium 4-styrenesulfonate. PVTPP-VPYM was obtained by quarternarization of a copolymer of VTPP and 4-vinylpyridine. Polymeric manganese(III) complexes (PMnVTPP, PMnVPTSPP, PMnVTPP-StSO3, and PMnVTPP-VPyM) were prepared from the polymers and manganese acetate. The acetate ligand in PMnVTPP can be easily substituted by another ligand such as Cl-, AcO-, OH-, and SCN-. The substitution reaction occurs in the interface between water and chloroform. The sulfonated homopolymer, PMnVPTSPP, cannot incorporate with anionic ligands because of the strong electrostatic repulsion. In the anionic copolymer, PMnVTPP-StSO3, the ligand substitution reaction with SCN ligand needs activation energy of 53 kJ/mol. In the cationic polymer complex, PMnVTPP-VPyM, the OH ligand can be easily substituted with the SCN ligand and the equilibrium constant of the reaction was estimated at 1.38 X 10(-3).