Synthesis and first structural characterization of hexa coordinated rhenium(I) tricarbonyl complex of 5,20-bis(p-tolyl)-10,15-bis(p-methoxyphenyl)-21-selenaporphyrin 3 are described. The Re(I) complex of 21-selenaporphyrin 3 was synthesized by treating free base 21-selenaporphyrin in 1,2-dichlorobenzene with Re(CO)5Cl at reflux for 7 h and analyzed using mass, NMR, FT-IR, UV-vis and electrochemical techniques. The first structure of metal complex of 21-selenaporphyrin was determined by X-ray single crystal analysis. The crystal structure revealed that the Re(CO)3 coordinates to two of the three inner nitrogens and one selenium to produce compound 3. The selenophene ring bent towards the Re(I) ion and the selenium is displaced by 0.41 Å from the mean plane of 24-atoms to coordinate with Re(I) ion in η1-fashion. The 21-selenaporphyrin is distorted in compound 3 compared to free base 21-selenaporphyrin. 1H and 13C NMR studies indicated that compound 3 exhibits fluxional behaviour in coordination mode of binding in solution. The compound 3 is highly stable and does not undergo decomplexation under acidic conditions. The absorption spectra showed three broad Q-bands and splitted Soret band and electrochemical studies indicated that compound 3 is stable under redox conditions.