The extremely high catalytic efficiency of undercoordinated noble metal adatoms is indeed fascinating, but its chemical and electronic origin remains yet puzzling. Incorporating the BOLS correlation theory [Sun, C. Q. Prog. Solid State Chem. 2007, 35, 1] into the high-resolution XPS measurements [Baraldi, A.; et al. New J. Phys. 2007, 9, 143; Bianchettin, L.; et al. J. Chem. Phys. 2008, 128, 114706] has affirmed the BOLS expectations that the broken bonds induce local strain and quantum trapping in addition to polarization of the otherwise conductive half-filled s-shell charge by the tightly-and densely-trapped inner electrons of the adatoms. Both the trapped and polarized states would be detectable from the density-of-states evolution of the valence and the core bands. The trapped states have been discovered at the bottom edges of Pt(5d 10 6s 0) 4f 7/2 and Rh 3d 5/2 bands, and the polarized states only present at the upper edge of Rh(4d 85 s 1) 3d 5/2 . It is suggested that the quantum trapping increases the electroaffinity and the polarization does oppositely. Therefore, the Rh adatom serves as a donor and the Pt adatom as an acceptor in the process of catalytic reaction.