The ability of a catalyst to accept or donate charge is the key to the process of catalytic reaction. However, the determination of the catalytic nature of a specimen as yet remains a great challenge. Here we report an effective yet simple method for this purpose based on the tight binding theory considerations and XPS monitoring of the evolution of valence and core electrons upon alloy formation. Firstly, we measured the valence and core band charge density of the constituent elements of Cu, Ag, and Pd and then the respective states upon alloy formation. A subtraction of the resultant spectrum of the alloy by the composed elemental spectra gives the residual that shows clearly the occurrence of charge trapping or polarization. We found that the valence and the core electrons of the CuPd alloy shift positively to deeper energies, opposite to the occurrences in the AgPd alloy. Findings clarify for the first time that CuPd serves as an acceptor due to quantum trapping and the AgPd as a donor because of charge polarization, which also explain why AgPd and CuPd perform very differently as important catalysts.