Reactions of the oxorhenium(V) complexes [ReOX 3 (PPh 3 ) 2 ] (X ϭ Cl, Br) with the N-heterocyclic carbene (NHC) 1,3,4-triphenyl-1,2,4-triazol-5-ylidene (L Ph ) under mild conditions and in the presence of MeOH or water give [ReOX 2 (Y)(PPh 3 )(L Ph )] complexes (X ϭ Cl, Br; Y ϭ OMe, OH). Attempted reactions of the carbene precursor 5-methoxy-1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazole (1) with [ReOCl 3 (PPh 3 ) 2 ] or [NBu 4 ][ReOCl 4 ] in boiling xylene resulted in protonation of the intermediately formed carbene and decomposition products such 2251 as [HL Ph ][ReOCl 4 (OPPh 3 )], [HL Ph ][ReOCl 4 (OH 2 )] or [HL Ph ][ReO 4 ] were isolated. The neutral [ReOX 2 (Y)(PPh 3 )(HL Ph )] complexes are purple, airstable solids. The bulky NHC ligands coordinate monodentate and in cis-position to PPh 3 . The relatively long ReϪC bond lengths of approximate 2.1 Å indicate metal-carbon single bonds.