Carbon fibers (CFs) supported platinum-cobalt (Pt-Co) electrocatalysts are prepared with H2 heat-treatment and used for hydrogen production by coal electrooxidation. Pt-Co alloy was formed and characterized by X-ray Diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The results show that the electrocatalystic activity and long-time stability of Pt-Co/CFs for coal electrolysis are enhanced with the introduction of cobalt. The PtCo/CFs (1:1) catalyst exhibits better catalytic activity than PtCo/CFs (7:3) and PtCo/CFs (3:7). The strong catalytic activities of the catalysts are attributed to synergistic effect between metallic alloying and modification of surface electrons of the bimetallic Pt-Co electrocatalysts.