XPS spectra of silver excited by synchrotron irradiation with energy same as Al K伪 X-ray has been measured. After filtering spectrum noise, the inelastic background starting from the lower binding energy of photoelectrons is removed by an iteration procedure. The energy loss spectrum for a single sub-shell photoelectron is then extracted from the Ag 3p XPS spectrum. Based on this single sub-shell photoelectron energy loss spectrum the effective energy loss function (EELF) is obtained by the extended Landau approach. Monte Carlo simulation with the derived EELF can reproduce well the experimental XPS spectrum.