Abstract: The preparation method of graphene/cobalt phthalocyanine (GR/CoPc) and its eletrocatalysis performance was presented. Synthesized by microwave-assisted method (DMEA as the solvent), with graphene (GR), anhydrous cobalt chloride and dicyanobenzene, the GR/CoPc complex was characterized by UV-vis, TEM, Raman, XRD and FT-IR. The GR/CoPc has CoPc distributed uniformly on its suface. EIS, CV, CA were used to study the electrocatalytic performance of the electrodes modified by GR/CoPc, CoPc and GR. The results show that GR/CoPc/GCE exhibits better electrocatalytic activity than CoPc/GCE and GR/GCE, towards the oxidation of NO<sub<2</sub<<sup<-</sup<. The GR/CoPc/GCE shows broad linear range (1.67～644.27μmol/L), good stability, anti-interference and reproducible, with detection limit of 0.6μmol/L.