Rhenium(V) complexes of 1H-benzimidazole (L), isolated from acidic media: (HL)2[ReOX5]·(H2O)n and [ReOLxXy(H2O)z](H2O)n (HL and L are protonated and deprotonated forms of benzimidazole; X = Cl-, Br-) were studied by means of IR spectroscopy, 1H NMR spectroscopy, and thermal analysis.