Four porous metalloporphyrinic framework materials, [(CH3)(2)NH2][Zn-2(HCOO)(2)(Mn-III-TCPP)]center dot 5DMF center dot 2H(2)O (1; H6TCPP = tetrakis(4-carboxyphenyl)porphyrin), [(CH3)(2)NH2][Cd-2(HCOO)(2)(Mn-III-TCPP)]center dot 5DMF center dot 3H(2)O (2), [Zn-2(HCOO)( Fe-III(H2O)-TCPP)]center dot 3DMF center dot H2O (3), and [Cd-3(H2O)(6)(mu(2)-O)(Fe-III-HTCPP)(2)]center dot 5DMF (4) were synthesized by heating a mixture of (MCl)-Cl-III-H4TCPP (M = Mn and Fe) and M' (M' = Zn or Cd) nitrate in a mixed solvent of DMF and acetic acid. Compounds 1-3 are built up from M-2(')(COO)(4) paddle-wheel subunits bridged by M-III-TCPP and formate ligands to form their 3D connections. The formate pillar heterogeneously connects with M and M' cations in 1 and 2 and homogeneously joins M' cations in 3. The mu(2)-O bridged Fe-III-HTCPP dimer performs as a decadentate ligand to link 10 cadmium cations for the formation of an interesting 3D coordination network of 4. The four porphyrinic frameworks present interesting catalytic properties in the selective epoxidation of olefins, oxidation of cyclohexane, and intermolecular aldol reaction of aldehydes and ketones.