A series of mixed beta-substituted porphyrins, 2,3,12,13-tetrakis(bromo/cyano/methyl)-5,7,8,10,15,17,18,20-octaphenylporphinatonickel( II)/copper(II), MOPPX(4)s (X = Br, CN and CH3; M = Ni(II) and Cu(II)) were examined in 24 different solvents with varying polarity. Among the porphyrins, MOPP(CN)(4) show enhanced solvent dependent optical absorption spectral features relative to other porphyrins, MOPPX4 (X = Br and CH3) and MTPPs. Although, MOPP(CN)(4) (M = Ni(II) and Cu(II)) have higher electron deficiency due to electron withdrawing beta-cyano groups, comparable solvent dependent absorption spectral features and opposite trend in their shift of bands relative to the corresponding MTPPBr8 were observed. The large red-shift of the absorption bands of Cu(II) and Ni(II)-mixed substituted porphyrins in polar solvents or nitrogenous bases has been suggested to the destabilization of the HOMO (b(2)) relative to b(1) (HOMO) level due to axial ligation of the polar solvents or nitrogenous bases with the core metal ions. The greater affinity of the core metal ions towards coordinating solvents or nitrogenous bases has been attributed to the electron deficient nature of the porphyrin pi-system and follow the order: MOPP(CN)(4) > MOPPBr4 > MOPP(CH3)(4) due to inductive/resonance effect of beta-substituents rather than the nonplanarity of the porphyrin ring.