A novel nanocomposite with a core-shell structure containing polystyrene (PS), polyaniline (PANI), and Au nanoparticles (NPs) was synthesized. The nanocomposite was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectroscopy (FTIR). Cyclic voltammetric experiments indicated that the nanocomposite had excellent redox ability in a wide range of pH values. The existence of Au NPs resulted in a higher electrical conductivity of the nanocomposite. As a model, glucose oxidase (GOD) was entrapped onto the nanocomposite-modified glassy carbon electrode (GCE) and applied to construct a sensor. The immobilized GOD showed a pair of well-defined redox peaks and high catalytic activity for the oxidation of glucose.