Thermal decomposition of double complex salt [Pd(NH3)4][PtCl6] in a helium atmosphere has been studied by ex situ X-ray diffraction, X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy. Statistical multivariate curve resolution approach to XPS and Auger spectra analysis was applied. This approach was compared with a convenient XPS analysis, demonstrating comparable results and its effectiveness in analysis of sample containing components with various oxidation states, but a little difference in composition. The result obtained allows the complex salt to use as a perspective single-source precursor in one-pot synthesis of PdPt alloy nanoparticles. To examine the precursor, thermal decomposition and shock of [Pd(NH3)4][PtCl6] were performed under various conditions in inert and reduction atmospheres and the final products were studied.