Low molecular weight saccharide complexes of vanadium of the type [VO(sacch)2]2-, were synthesized for the first time by simple and reproducible methods in nonaqueous media. These reactions yielded water-soluble products which were characterized by various analytical and spectroscopic techniques and by cyclic voltammetry. The vanadyl d-glucose complex 1 shows a resemblance to a natural vanadium-binding component vanadobin, isolated from the tunicate Ascidia sydneiensis samea. All the saccharide complexes are stable in solution for long periods under ambient conditions without being oxidised and showed no hydrolysis in the pH range 2-12. All the saccharide complexes reported in this paper show evidence for the V(IV) species. © 1994 Elsevier Science B.V. All rights reserved.