 This study developed a system that combines light field and in situ irradiated x-ray photoelectron spectroscopy to observe the charge transportation in a Li-S battery. It was found that amorphous TO2-PEX nanoparticles and nickel nanoparticles act as both oxidation and reduction sites, promoting the decomposition and nucleation of Li-2S, respectively. This method can provide a more comprehensive understanding of the sulfur electrochemistry in Li-S batteries. This article was authored by Pimpeng Zhang, Yaizhao, Yukun Li, and others.