Hydrogen peroxide (H2O2), an important representatives of reactive oxygen species, its aberrant expression is related to many diseases including cancers. Therefore, it is very significant to design the reliable method for real-time detection endogenous H2O2. Herein, we prepared a poly (azure I)/crumpled graphene (cGN) modified electrode by electro-polymerization method. Results showed that this electrode presented obvious electrocatalytic effect on the reduction of H2O2. Amperometric method was employed to monitor H2O2, and the amperometric response exhibited a good linear relationship with its concentration in the range of 8.0×10 -6~1 .25×10 -3 mol/L, the detection limit reached to 6.7×10 -7 mol/L (S/N = 3).Furthermore, this modified also displayed the good selectivity, long-term stability and high anti-interference ability. Excitingly, the established method could be successfully used to detect H2O2 in human serum samples, and measured H2O2 secreted from living MCF-7 cells. It could have potential in cancer diagnosis.