The instable structure of Pt-based high-indexed facets (HIFs) facile reconstructed is a key obstacle for further practical applications because of its high surface energy and amounts of undercoordinated surface atoms. Herein, a strategy to advance the fundamental surface study on Pt-based HIFs materials is addressed by implanting non-noble metal or nonmetals as “active auxiliaries” into the near-surface of noble metal nanocrystals bounded with HIFs to engineer a stable structured catalyst. Then the Mo/Pt₃Mn catalysts serving as proof-of-concept examples are designed and show enhanced catalytic performance of ethylene glycol (EG). According to the electrochemical in situ Fourier transform infrared spectroscopy results, the Mo modified Pt₃Mn alloys with HIFs promote not only the C–C cleavage of EG but also the direct conversion of COH_X to CO₂, without the formation of CO_L poison species. In this case, the Mo/Pt₃Mn catalysts show the greatly significant increase of the catalytic activity in copamprison with Pt₃Mn CNC and the commercial Pt/C, as well as the enhanced stability. The high-resolution transmission electron microscopy and X-ray photoelectron spectrum assisted by Ar surface etching experiments accompanied by density functional theory calculations are further used to explore the structure–performance relationship of Mo/Pt₃Mn CNC for electro-oxidation of EG. This study addresses a promising strategy to fabricate a stable structured catalysts, which will elucidate a very promising methodology for developing Pt-based catalysts for further application of the fuel cell.