Six Mn-III(porphyrin)-based porous coordination polymers, Mn-III(F(5)CPp)-Mn-II (CP1, F(5)CPp=5-(pentafluorophenyl)-10,15,20-tri(4-carboxyphenyl)porphyrin dianion), Mn-III(F(5)CPp)-Co-II (CP2), Mn-III(F(5)CPp)-Ni-II (CP3), Mn-III(F(10)CPp)-Mn-II (CP4, F(10)CPp=5,15-bis(pentafluorophenyl)-10,20-bis(4-carboxyphenyl)porphyrin dianion), Mn-III(F(10)CPp)-Co-II (CP5), and Mn-III(F(10)CPp)-Ni-II (CP6), were prepared and characterized. The precursors were identified by UV-Vis, GC-MS, infrared spectra and elemental analysis in the procedures of Mn-III(porphyrin)-based polymers synthesis. CP1, CP4, CP3 and CP6 are amorphous aggregation supported by SEM, TEM and powder XRD. CP2 and CP5 are rod-like microcrystalline particles supported by powder XRD and SAED. These polymers exhibit high catalytic activities and selectivities toward the oxidation of ethylbenzene to acetophenone in quantitative over 70 % yields, and can be reused by filtration with only slight decreasing of catalytic activities.