Glucose detection is extremely necessary in several zones like foodstuff industries, analytical field, clinical diagnostics and biotechnology. In particular, diabetes mellitus which is a common chronic disease that threatens to the human health. To avoid this trouble, glucose recognition is significant. In this work, a novel vanadium dioxide (VO2) was developed by means of basic thermal decomposition method and the nanocomposites such as VO2/2%PVA, VO2/4%PVA and VO2/6%PVA were also synthesized by using PVA (Poly vinylalcohol (wt% = 2, 4 & 6)) as a capping agent. The constructed nanocomposites were exploited for non-enzymatic glucose detection in 0.1 M of NaOH medium and showed better electro-catalytic activity than, PVA, VO2, VO2/2%PVA and VO2/4%PVA modified electrodes. The built glucose biosensor of vanadium dioxide-PVA nanocomposites possess high selectivity, stability, sensitivity (614.35 µA mM−1 cm−2), lowest detection limit (1.45 µM), low cost and minimal effort for the quick identification of glucose.