A systematic study of the synthesis of V2O5 nanostructured materials using macromolecular PS-co-4-PVP(VCl3)y and chitosan·(VCl3)y complexes is presented. It is demonstrated that various coordination degrees of the metal into the polymeric chain specifically influence the product formation after pyrolysis. PS-co-4-PVP·(VCl3)y and chitosan·(VCl3)y complexes were prepared by simple coordination reaction of VCl3 with the respective polymer in molar ratios 1 : 1, 1 : 5, and 1 : 10 metal/polymer and characterized by elemental analysis, IR spectroscopy, and TGA/DSC analysis. Solid-state thermolysis of these precursors at several temperatures under air results in nanostructured V2O5 using all precursors. The size and shape of the nanostructured V2O5 depend on the nature of the polymer. For the chitosan·(VCl3)y precursors sub-10 nm nanocrystals are formed. The calcination process, involved in the preparation method, produces V2O5 with photoluminescence in the visible light region, suggesting the possible application in oxygen sensing devices.