The complex (quinap)Re-I(CO)(3)Cl, with quinap = 1-(2-diphenylphosphino-1-naphthyl)isoquinoline, shows a luminescence at lambda(max) = 582 nm with phi = 0.12 and tau = 1.4 mus in solution (e.g., CH2Cl2) at r.t. It is suggested that this emission originates from a Re-I to quinap metal-to-ligand charge transfer triplet. CD 2002 Published by Elsevier Science B.V.