The rapid and precise detection of hydrogen peroxide has recently been a hot research in non-enzymatic electrochemical sensors. Herein, peanut shell-like Cu-Mo2C/Mo3P/C composite was simply prepared by in-situ simultaneous phosphorization and carbonization of [Cu(P4Mo6)]-based metal–organic framework (MOF) under N2/H2 atmosphere. Then, the above nanomaterials were deposited on glassy carbon electrode (GCE) surface through facile drop coating method, thus fabricating a highly efficient non-enzymatic H2O2 electrochemical sensor. In phosphate buffer solution (PBS, pH = 7.4), the Cu-Mo2C/Mo3P/C/GCE exhibits high sensitivity (653.2 μA mM−1 cm−2) and low detection limit (37 nM) to H2O2. Its amperometric response is 1.94, 3.27 and 4.71 times bigger than that of Mo2C/Mo3P/C/GCE, Mo3P/GCE and Mo2C/GCE. Such good electrochemical sensing performance is mainly ascribed to the synergism of unique microstructure, platinum-like Mo2C and Mo3P co-combination, together with copper and carbon dual-doping. Moreover, it can realize the satisfactory detection of H2O2 in human serum, disinfectant and contact lens solution, indicating the potential application in the fields of environmental monitoring and biochemical analysis.