In situ prepared lithium arylselenolates {LiSePh, LiSe(2,6-Me 2 Ph), LiSe(2,4,6-Me 3 Ph)} or -tellurolates {LiTePh, LiTe(2,6-Me 2 Ph), LiTe(2,4,6-Me 3 Ph)} react with [ReOCl 3 (PPh 3 ) 2 ] and (NBu 4 )Br in good yields under formation of rhenium(V) complexes of the composition (NBu 4 )[ReO(L) 4 )]. The first oxidorhenium(V) complex with four monodentate phenolato ligands, [ReO(2,6-Me 2 Ph) 4 ] À , was prepared and isolated in crystalline form. This allows a comparison of experimental and computational data of a full series of such compounds with basal O, S, Se and Te donor atoms. Similar reactions with [ReCl 3 (PPh 3 ) 2 (CH 3 CN)] or [ReCl 3 (PMe 2 Ph) 3 ] give trigonal bipyramidal rhenium(III) complexes of the compositions [Re(PPh 3 )(L) 3 (CH 3 CN)] or [Re-(PPh 3 ) 2 (L) 3 ] depending on the chalcogenolate applied. The reported oxidorhenium(V) and rhenium(III) complexes were fully characterized by spectroscopic methods and X-ray diffraction. The bonding situation in the rhenium(V) and rhenium(III) chalcogenolates was assessed through density functional theory calculations based on the quantum theory of atoms in molecules (QTAIM), natural bonding orbital (NBO) analysis, charge analysis, the electron localization function (ELF) maps and topological descriptors at the {3,À 1} critical points such as metallicities. Expectedly, the ionicity of the rhenium-chalcogen bonds decreases according to all three applied charge models from O to Te. Generally, the ReÀ Se and ReÀ Te bonds are more directional in the Re(III) complexes than in the oxidorhenium(V) compounds.