Modified electrodes with metal or metal oxides nanoparticles are particularly appealing to improve sensor performances and fabricate miniaturized devices, as required also in glucose detection. A Pt electrode modified by drop casting of a novel nanostructured film based on silver nanoparticles (Ag-NPs) capped in a commercial nontoxic polyvinyl alcohol (PVA) matrix is proposed here as a valid alternative to classical glucose (bio)sensors. The extensive electrochemical and spectroscopic characterization by X-ray Photoelectron Spectroscopy (XPS) of this advanced nanomaterial is presented to study its response to glucose and to investigate the chemical nature of deposited Ag.