The invention belongs to a technical field of preparation of electrochemical electrode materials, and provides an electrochemical sensor for simultaneously detecting guanine and adenine. The electrochemical sensor based on copper@nickel/nitrogen, boron doped reduction graphene oxide simultaneously detects guanine and adenine. The electrochemical sensor is based on copper@nickel/nitrogen, boron doped reduction graphene oxide composites, and prepared by modifying a surface of glassy carbon electrode. The electrochemical sensor has high sensitivity and selectivity, good stability and reproducibility, and the electrode modification process is simpler. The preparation method comprises: based on the copper@nickel/nitrogen, boron doped reduction graphene oxide composites, preparing the nitrogen,boron doped reduction graphene oxide N, B-rGO by hydrothermal method, and preparing the copper@nickel/nitrogen, boron doped reduced graphene oxide Cu@Ni/N, B-rGO; and preparing an electrode. The invention improves the sensitivity of the electrode and makes the electrode modification process simpler. The electrochemical sensor is used to construct a sensing system for simultaneous detection of guanine and adenine in adenosine, which significantly increases electrode selectivity.