Oxorhenium(V) complexes of -diketonate systems have been synthesized and isolated in pure form. The red complexes n-Bu 4 N[ReO(R 1 COCHCOR 2 )Cl 3 ] (acac, R 1 ¼R 2 ¼CH 3 ; bzac, R 1 ¼CH 3 and R 2 ¼C 6 H 5 ; bzbz, R 1 ¼R 2 ¼C 6 H 5 ) have been characterized by elemental analyses, spectroscopic and other physico-chemical tools. One complex, n-Bu 4 N[ReO(bzbz)Cl 3 ] (1c) has been subjected to single-crystal X-ray analysis. In the structure of the anion, the metal has a six-coordinate octahedral environment in which the bidentate -diketone ligand is cis and trans to the terminal oxygen.