Using density functional theory, we have studied the effects on structural and electronic consequences (including HOMO–LUMO energy gaps, vertical ionization potentials (IP v ), and vertical electron affinities (EA v )) of the following two factors: (a) meso- and β-substituents acting as inductive donors (CH 3 ), inductive acceptors that are electron-donating through resonance (Br), inductive electron acceptors (CF 3 ), and resonance enabled acceptors (NO 2 ); and (b) complete replacement of pyrrole nitrogens with P-atoms. The principal results of the study are: (1) For the bare Ni-porphyrin, the solvents were found not to affect the HOMO–LUMO gaps but to change the IP v and EA v noticeably. (2) In the series CH 3 →Br→CF 3 →NO 2 the HOMO–LUMO energy gaps, IP v , and EA v increase for both meso- and β-substituents. The ruffling distortion of the porphyrin core is retained, and becomes stronger for the two acceptor groups. In general, effects of meso-substituents on the ruffling distortion of the porphyrin core is more pronounced. (3) Most significantly, complete replacement of pyrrole nitrogens in the NiP with phosphorus atoms produces the species, NiP(P) 4 , with the structural and electronic features drastically different from the original NiP. This implies that NiP(P) 4 can possess interesting and unusual novel properties, including aromaticity and reactivity, leading to its various beneficial potential applications. Furthermore, NiP(P) 4 high stability both in the gas phase and different solvents was shown, implying the feasibility of its synthesis.