A electroanalytical method was proposed for the determination of bisphenol A (BPA) based on polyvinylpyrrolidone-graphene composite modified glassy carbon electrode (PVP-GR/GCE). Morphology and property of PVP-GR/GCE were examined by scanning electron microscopy and cyclic voltammetry. Electrochemical performance of PVP-GR/GCE for detection of BPA has been investigated by second-order derivative linear sweep voltammetry. The linearity range, detection limit, repeatability, reproducibility, stability, selectivity and sample adding standard recovery under the optimal condition were researched. The PVP-GR/GCE showed enhancement effect on the detection of BPA. Influencing factors including the amount of casted PVP-GR, pH of buffered solution, accumulation potential as well as time were optimized. The results showed PVP-GR was of the properties of GR, with the dispersibility in water solution better than that of GR; the oxidation peak current of K3[Fe(CN)6] was greatest in PVP-GR/GCE, which indicated the adding of PVP improved GR water solution, and enhanced the electrochemical property. Under optimal conditions, a linear relationship between concentration of BPA and response current was obtained in the range of 0.01~0.40 μmol/L and 0.40~60.00 μmol/L with the detection limit of 8.0 nmol/L (S/N：3). The PVP-GR/GCE exhibited good selectivity, sensitivity, reproducibility and high stability. The PVP-GR/GCE was successfully applied in the determination of BPA in real samples with the recovery of 97.3%~105.2 %.