meso-Tetrakis(4'-diethoxyphosphorylphenyl)porplirin (H-2-TPhPP) was synthesized via modified Lindsey method with higher yield (50%) as compared to reported methods. H2TPhPP exhibited 120-140 mV anodic shifts in first ring redox potentials as compared to H2TPP. Similarly, anodic shifts of MTPhPP (M = Ni(II), Cu(II), and Zn(II)) were 70-210 mV in first ring oxidation potentials and 80-120 mV in first ring reduction potentials, as compared to corresponding MTPPs due to the strong electron-withdrawing nature of diethoxyphosphoryl substituents.