Improving the complete ethanol electrooxidation on Pd-based catalysts in alkaline media has drawn widely attention due to the high mass energy density. However, the weak adsorption energy of CH3CO* on Pd restricts the C-C bond cleavage. Inspired by the molecular orbital theory, we proposed the d-state-editing strategy to construct more unoccupied d-states of Pd for the enhanced interaction with CH3CO* to break C-C bonds. As expected, the reduced number of eg electrons and more unoccupied d-states of Pd successfully formed on as-prepared porous RhAu-PdCu nanosheets (PNSs). Theoretical calculations show that the optimized d-states of RhAu-PdCu PNS can effectively improve the adsorption of CH3CO* and drastically reduce the energy barrier of C-C bond cleavage, thus boosting the complete oxidation of ethanol. The charge ratio of C1 pathway on RhAu-PdCu PNSs is 51.5%, more than 2 times higher than that of Pd NSs. Our finding provides an innovative perspective for the design of highly-efficient noble-based electrocatalysts.