Among numerous metal oxide based nanocomposites, the polymer incorporated nanocomposites has received fascinated attention as promising electrode materials for inexpensive nonenzymatic glucose sensor. In this study, development of a sensitive and selective glucose sensor was fabricated using molybdenum trioxide (MoO3) via sol–gel method. The synthesized molybdenum trioxide was modified with capping molecule (wt% = 2, 4 and 6) PVP(poly-(vinylpyrrolidone)). The morphology and microstructure of the samples were examined by UV–vis diffuse reflectance spectroscopy (UV–vis-DRS), Fourier Transmission Infra-Red spectroscopy (FT-IR), Raman spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), high-resolution transmission electron microscopy (HR-TEM), X-ray photoelectron spectroscopy (XPS) and brunauer-emmett-teller (BET) analysis. The fabricated PVP modified MoO3 nanocomposites were utilized as a non-enzymatic glucose sensor in 0.1 M NaOH medium at a pH of 12 at room temperature. The synthesized nanocomposites have magnificent performance towards the detection of glucose. This is owing to enhancement effect as well as mesoporous nature of MoO3/(6%)PVP nanocomposite. The sensor demonstrates a low detection limit of 0.022 µM with a sensitivity of 86.42 µA mM−1 cm−2. It also exhibits good selectivity, stability and simplicity for the rapid detection of glucose. This sensor was opted for the determination of glucose in real sample as well.