A novel nanomaterial composed of copper and carbon nanofibers (CuCNFs) decorated with Ag-doped TiO2 (Ag-TiO2) nanoparticles was prepared through electrospinning, carbonization and solvothermal treatment. The composites were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and electrochemical impedance spectroscopy (EIS). The obtained composites were mixed with laccase and Nafion to construct novel hydroquinone biosensor. The electrochemical behavior of the novel biosensor was studied using cyclic voltammetry (CV) and chronoamperometry. The results demonstrated that the biosensor possessed a wide detection linear range (1.20-176.50 mu M), a good selectivity, repeatability, reproducibility and storage stability. This work provides a new material to design more efficient laccase (Lac) based biosensor for hydroquinone detection.