Sulfur and sulfide are very promising candidates for electrochemical energy storage in electric vehicles and grid-scale storage due to their high theoretical capacity, low cost, and abundance. Although tremendous efforts have been devoted to sulfur and sulfide related batteries in recent years, they are still facing several challenges that need to be addressed before they can be widely adopted. Challenges including polysulfide shuttling effect in metal-sulfur batteries and electrochemical/interphase stabilities in sulfide solid-state electrolytes hindered their practical applications. Various techniques and strategies have been developed to address the above-mentioned challenges. However, revealing a next-level understanding of sulfur species interactions and speciation, using multimodal X-ray measurements to study the interaction temporally and spatially is still lacking. Here, we employed multimodal X-ray measurements including in situ sulfur K-edgeX-ray absorption spectroscopy, X-ray diffraction, and transmission X-ray microscopy to reveal electronic structure, crystal structure, morphology of sulfur species during battery cycling. Specifically, using operando sulfur K-edge X-ray absorption and X-ray diffraction, we obtained real-time and chemical information of sulfur species occurring at the sulfur cathode during lithium-sulfur battery operation. In the case of sulfide solid-state electrolytes, we explored the capacity loss mechanism in LiNi0.8Mn0.1Co0.1O2 cathodes when using argyrodite Li6PS5Cl sulfide solid electrolytes. Nickel K-edge X-ray absorption spectroscopy and transmission X-ray microscopy showed the cracking formation and heterogeneity in oxidation states for LiNi0.8Mn0.1Co0.1O2 cathodes using Li6PS5Cl solid-state electrolytes. In summary, we elucidated the dynamic changes in sulfur and provide insights on designing next-generation sulfur and sulfide related batteries.