This study analyzed the composition and uranium valence of pitchblendes sampled from the hydrothermal Guidong and Zhuguang uranium deposits of the middle Nanling metallogenic belt, Southern China using X-ray photoelectron spectroscopy (XPS). A revolutionary discovery is that the uranium not only exists in the forms of tetravalent and hexavalent uranium oxides, but also occurs in the form of native uranium. This is the first discovery of the existence of native uranium in nature. It greatly helps to reveal the origin of hydrothermal mineralization of uranium, and also has great significance for studying the thermal energy, formation and evolution of the earth.