Abstract <p>In this study, we developed and validated an analytical method by combining electromembrane extraction (EME) with voltametric analysis for accurately quantifying Zolpidem. We optimized key EME parameters, including solvent composition, voltage, pH adjustments and extraction time. Zolpidem was transferred from a donor solution (pH 5) to an acceptor solution (pH 13) using a hollow fiber in 1-octanol as a membrane, driven by a 60 V voltage for 25 minutes, ensuring precise and selective extraction. For voltametric determination, poly, (pyrrole) (PPY) was synthesized with consecutive cyclic voltammetry (CV) in monomeric solution (containing 10 mmol L^-1monomer PY, 0.5 mol L^-1perchloric acid media) in the presence of vulcan (VU) on the surface of a screen-printed electrode (SPE). Scanning electron microscopy was used to characterize the Vulcan/poly pyrrole nanocomposite (PPY–VU). The PPY–VU/SPE was used as the modified electrode for the electrochemical determination of Zolpidem (ZP) tartrate voltametric techniques in a Britton-Robinson (BR) buffer (pH 5). In comparison with SPE, VU/SPE and PPY/SPE, the PPY–VU/SPE was much more efficient for ZP oxidation. Calibration curves with good linearity were obtained in the concentration range of 0.1-50 µmol L^-1 using the voltametric technique with the detection limit of 0.5 nmol L^-1. Finally, the PPY–VU/SPE was successfully used to determine ZP in tablet dosage form, urine and plasma. The result of the assay of ZP tablets using proposed electrode was in agreement with the result obtained from analysis of the same samples (same batch number) by method reported in the current United States Pharmacopoeia (USP).</p> Graphic abstract <p></p>