We report the synthesis, characterization, and photophysical properties of a series of rhenium(l) polypyridine maleimide complexes [Re(N-N)(CO)(3)(py-3-mal)](CF3SO3) [N-N = 1,10-phenanthroline, phen (1), 2,9-dimethyl-1,10-phenanthroline, 2,9-Me-2-phen (2), 3,4,7,8-tetramethyl-1,10-phenanthroline, 3,4,7,8-Me-4-phen (3), 4,7-diphenyl-1,10-phenanthroline, 4,7-Ph-2-phen (4), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 2,9-Me-2-4,7-Ph-2-phen (5), 2,2'-biquinonine, biq (6); py-3-mal = N-(3-pyridyl)maleimide]. The X-ray crystal structure of complex 2 has been investigated. Upon excitation, the complexes exhibit intense and long-lived photoluminescence in fluid solutions at 298 K. The emission wavelengths range from 514 to 654 nm, and the emission lifetimes fall in the microsecond time scale. The luminescence is assigned to originate from a metal-to-ligand charge-transfer MLCT [dpi(Re) --> pi*(diimine)] triplet excited state, As the maleimide group can react with the sulfhydryl group to form a stable thioether moiety, these complexes have been used as thiol-specific luminescent labels for a thiolated oligonucleotide, glutathione, and bovine serum albumin and human serum albumin, The photoluminescence properties of the labeled biological species have also been investigated.