Equimolar interaction of VO(OPr i) 3 with N-phenyldiethanolamine (H 2 L) affords the dimeric complex [VO(L)(µ-OPr i)] 2 (1), which on reaction with different glycols yields a new class of oxovanadium(V) complexes of the type: VO(L)(OGOH) (where L = C 6 H 5 N(CH 2 CH 2 O-) 2 and G = G 1 (CMe 2 CH 2 CH 2 CMe 2) 2, G 2 (CHMeCH 2 CMe 2) 3, G 3 (CH 2 CMe 2 CH 2) 4, G 4 (CH 2 CEt 2 CH 2) 5, G 5 (CHMeCHMe) 6, G 6 (CMe 2 CMe 2) 7), featuring N-phenyldiethanolaminate and glycolate moieties. Complexes (2)-(7) react with Al(OPr i) 3 to afford novel heterobimetallic coordination complexes of the type: VO(L){(OGO) Al(OPr i) 2 } (G = G 1-G 6). All these complexes have been characterised by elemental analyses and molecular weight measurements. Spectroscopic (IR, UV-Vis and (1 H, 27 Al, 51 V) NMR) properties of the new complexes have been investigated and their plausible structures suggested.