Electricity production from clean energy sources has gained attention during these decades. However, many power plants worldwide still use coal and natural gas as raw materials, which generates toxic gases, especially CO and CO2. To deal with this problem, transforming generated CO into another useful precursor before sup-plying it to the chemical process is a good idea. One of the most effective approaches is WGSR using a highly effective catalyst. In this work, we elucidate the insight information of PtPdRhFeCo HEA(1 1 1) surface improving the catalytic efficiency of Pt(1 1 1) surface. Interestingly, the homogenous form of electron distribution along Pt (1 1 1) surface is changed to heterogeneous forms creating unique electronic properties in which the electron donor and acceptor species exist simultaneously. The weakening interaction of CO corresponding to the strengthening interaction of CO2 on HEA(1 1 1) surface are advantages to preventing CO poison and trapping the CO2 after the WGSR. Moreover, the HEA(1 1 1) surface can thermodynamically promote the dissociation of H2O in pre-WGSR, creating active species of H*, O*, and OH* supplying to further the WGSR process. Nevertheless, consideration of PES along WGSR demonstrates that all possible pathways, including carboxyl, redox, and formate pathways along HEA(1 1 1) surface, are significantly improved by enhancing the thermodynamic driving force producing CO2.