Rhenocene, Re(?75-C5H5)2, has been generated by photolysis of Ref^-CsHs^H isolated in nitrogen and argon matrices at 12 K, and has been studied by laser-induced fluorescence with a pulsed tunable laser. The emission lifetime of the lowest LMCT excited state is (71.9 ± 1.3) ns in nitrogen and (69.3 ± 1.4) ns in argon matrices. The emission and excitation spectra are far simpler and much better resolved than the UV/vis absorption spectrum, because the laser selects individual sites/conformers in the matrix (or groups of sites with very similar absorptions). Vibrational progressions are detected which are based on the ring-metal-ring stretching mode, v4, and combinations of that mode with the symmetric ring breathing mode, v2, and the symmetric C—H deformation mode, v3. In the LMCT excited state, there is an increase in v4 of 5% and a decrease in v3 (9%) and v2 (3%), consistent with transfer of an electron from a ligand jr-orbital to a metal—ligand bonding orbital.