It is difficult to get accurate, precise and reliable analytical data when using X-ray fluorescence spectrometry (XRF) to determinate sulfur in geological sample. The possible ways to improve sulfur determination accuracy are discussed. Sulfur, and the major, minor and trace elements in soils were determined by polarization energy dispersion XRF (EDXRF) spectrometry and the element profiles and vertical distribution were obtained. Based on this, replacement of two short-term vegetation soil profiles was studied. Significant correlations among the vertical distribution of soil organic carbon content (TOC), organic carbon stable carbon isotopes (δ 13C) and several elements were found. The study showed that the EDXRF method can be well applied to element soil geochemical cycle and carbon cycle researches.