Hafnium doped zinc oxide(Hf-ZnO) was prepared from tetrachloride hafnium (HfCl4) and zinc nitrate by hydrothermal method. Tyr/Hf-ZnO/CS/GCE was obtained by modifying tyrosinase (Tyr)、Hf-ZnO and chitosan (CS) onto Glassy carbon electrode (GCE). The structure and properties of the Hf-ZnO was characterized by FESEM, XRD, DLS and XPS. Electrochemical tests were conducted on the modified electrode Tyr/Hf-ZnO/CS/GCE by cyclic voltammetry (CV) and chronoamperometry (IT). The results showed that Tyr/Hf-ZnO/CS/GCE electrode had the best detection ability for catechol at a low potential of -50 mV and pH 5. The linear range of catechol detection was 0.5~47 μmol/L, the sensitivity was 195 μA/(mmol/L), and the detection limit was 0.1215 μmol/L(S/N=3). In addition, the biological electrode has good stability and repeatability, and can effectively avoid the electrical activities similar with catechol interference of urea, dopamine, and ascorbic acid.