The coordination chemistry between copper acetate [Cu2(OAc)4] and 5,10,15,20-tetra-4-pyridyl-21H,23H-porphine (porphyrin, H2TPyP) is found to give rise to either a 2D metal-organic framework (MOF) [Cu(TPyP)Cu2(O2CCH3)4] or a 3D MOF [Cu(TPyP)CuCl2]·2.5TCE·7H2O], depending on the choice of solvent. The 2D MOF can be made into a film, which was doped with 7,7,8,8-tetracyanoquinodimethane (TCNQ), and the electrical conductivity of the thin film was increased by 3 orders of magnitude with respect to that of the undoped Cu-MOF. The formation of a charge-transfer complex between TCNQ and the 2D Cu-MOF also imparts stronger paramagnetic properties than for the undoped MOF.