A glassy carbon electrode was modified with a composite made from gold nanoparticles and silk fibroin whose surface was further modified with amino-terminated G4 poly(amidoamine) dendrimer. This electrode shows distinct electrochemical response to bisphenol A (BPA). Electrochemical impedance spectroscopy was used to characterize the surface. The electrode displayed improved adsorption capacity and an increased response to BPA, compared to a surface without modification. Under the optimal detection conditions, the respeonse is linear in the concentration range from 1 nM to 1.3 μM, the correlation coefficient is 0.9991, and the detection limit is 0.5 nM (at an S/N of 3). The method was applied to the determination of BPA in water samples, and the recovery was in the range from 97% to 105%.