The structural features of 24 mononuclear octahedral monooxo d2-Re(V) complexes with single charged oxygen atoms of bidentate chelate (O, N) ligands (Ln) of the general formula [ReO(Ln)2(Lmono)] (where Lmono is a monodentate ligand) containing six-membered chelate rings ReNC3O are discussed. The O(Ln) atoms, with three exception, are in the trans positions to the O(oxo) ligands. In the two complexes, the oxygen atoms of the acido-ligand OMe− occupy the trans positions to the oxo ligands, and in the third, it is occupied by the O atom of the neutral H2O ligand. In the case of complexes [ReO(Ln)2(Lmono)] with five-membered chelate cycles ReNC2O, the structures of three complexes with Lmono ligands in the trans positions to oxo ligands are also known: one with Lmono = Cl− and two with Lmono = OMe−.