We report on the time evolution of the sodium tetrachloroaurate (NaAuCl(4)) chemical properties as a function of soft X-ray exposure in a dried sample on a silicon surface using X-ray photoelectron spectroscopy (XPS). Our investigations provide mechanistic insight into the photoreduction kinetics from Au(III) to Au(I) and then Au(I) to Au(o). We unambiguously show that XPS photoreduction occurs in stepwise fashion via the Au(I) state. Both photoreduction steps undergo first-order kinetics.