A new synthesis procedure has been developed for the preparation of oxo-rhenium(V) porphyrins using melted benzoic acid. Here we have demonstrated this method using three representative compounds namely O=ReV(TPP)(OOCPh) (1), O=ReV(TMP)(OOCPh) (2), and O=ReV(TCP)(OOCPh) (3) [where TPP = 5,10,15,20-meso-tetraphenylporphyrin, TMP = 5, 10, 15, 20-meso-tetra(p-methoxy)phenylporphyrin and TCP = 5, 10, 15, 20-meso-tetra(p-chloro)phenylporphyrin]. The yield percentage is higher than any other method reported earlier. All the compounds were well characterized by C, H and N microanalysis, ESI-MS, IR, UV–vis and 1H NMR spectroscopic techniques. On treating with mild bases like pyridine, imidazole, dil. NH4OH compound 1 instantly gets converted to µ-oxo bridged dimeric oxorhenium(V) complex µ-O-[ReO(TPP)]2 (4). The electrochemical behavior of the synthesized compounds has been examined by the cyclic voltammetric method. Theoretical calculations like geometry optimization, electronic energy, frequency, and frontier molecular orbital (FMO) energy level diagram for compound 1 have been investigated by Density Functional Theory (DFT) method. The experimentally calculated HOMO-LUMO energy gap and the experimental electronic spectrum were found to agree well with the value obtained from DFT studies.