The dithia/diselena meso-tetraarylporphyrins have a lesser tendency to form metal complexes because of the larger size of the heteroatom(s), which shrinks the cavity size, and the heteroatoms also have poor coordinating ability to bind metal ions. The first example of a rhenium(I) tricarbonyl complex of 21,23-diselenaporphyrin was synthesized by treating 5,10,15,20-tetra-p-tolyl-21,23-diselenaporphyrin with Re(CO)(5)Cl in chlorobenzene at reflux temperature and its structural properties were compared with our earlier reported rhenium(I) complex of tetraaryl-21,23-dithiaporphyrin. The crystal structures of rhenium(I) complexes of diheteroporphyrins revealed that the Re-I ion binds to both the Se/S atoms and one of the N atoms of the porphyrin core along with three terminal carbonyl groups in an octahedral fashion. The rhenium(I) complexes of 21,23-diheteroporphyrins are stabilized by a large counterion, the trichloro-bridged dirhenium(I) ion. We also present a detailed account of the spectral and redox properties of rhenium(I) tricarbonyl complexes of 21,23-diheteroporphyrins.