© 2016 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.Rhenium(i) N-heterocyclic carbene (NHC) complexes of the type fac-[Re(CO)3(NHC)L] with either azide or triazolate ancillary ligands L and pyridyl or pyrimidyl substituted imidazolyl units have been prepared and structurally characterised, and their photophysical and photochemical properties studied. All of the complexes exhibit phosphorescent emission from triplet metal-to-ligand (3MCLT) excited states, typical of tricarbonyl Re(i) complexes, with the triazolate bound complexes having higher quantum yields and longer decay lifetimes compared to the azide bound complexes. The complexes containing pyridyl substituted imidazolyl units are photoreactive when dissolved in acetonitrile and undergo photochemical CO dissociation, the rate of which is significantly greater in the azide cf. triazolate complex. The photochemical mechanism of the azide/pyridyl complex was analysed and appears to give the same products, albeit with different ratios, to previously reported complexes where L is a halide. A reaction mechanism is proposed.