In this work, an effective anode electrocatalyst prepared by distribution of PtCu nanoparticles (PtCu NPs) on poly(EDOT-pyridine-EDOT) (poly [BPE]) and poly(EDOT-pyridazine-EDOT) (poly [EPE]) composited double-layered hollow carbon spheres (DLHCs) via polyol method. The structural and morphological analysis demonstrated the uniform dispersion of PtCu NPs on the poly(EPE)/DLHCs and poly(BPE)/DLHCs composite surface with an averaged diameter of 2.13 and 2.19 nm, respectively. To further investigate the electrocatalytic performance of as-synthesized hybrid catalysts, cyclic voltammetry and amperometric i-t were conducted. It was found that the poly(EPE)/DLHCs/ PtCu catalyst had favorable properties such as large electrochemical specific surface area (269.05 m 2 g À1 ) and high mass activity for methanol (1304.93 mA mg À1 ) in the acidic electrolyte, which were 1.94 and 1.23 times higher than that of poly(BPE)/DLHCs/PtCu. The low onset potential and the high oxidation current density occurred in poly(EPE)/DLHCs/PtCu, which could be contributed to the superior electronic conductivity, abundant N, S and O atoms and OH ads promoters on the poly(EPE)/DLHCs as well as the effective interaction of binary composite to PtCu NPs, implying that poly(EPE)/DLHCs/PtCu could be a promising anodic catalyst in methanol oxidation.