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Detailed study of multicomponent systems in solid-state as well as in solution using X-ray diffraction and X-ray spectroscopy is one of the most common topics in modern materials chemistry. 5-6 component high-entropy alloys such as fcc- and bcc-structured AlxCoCrFeNi and fluorescent nanoparticles based on fluorite-structured SrF2 doped by rare-earth metals in organic solutions have high complexity and their local structure cannot be resolved using only diffraction. X-ray absorption spectroscopy should be applied to understand peculiarities in their local structure and make a link between structure on short and long ranges and their macroscopic properties. Here, based on two representativee examples, we discuss how a combination of several X-ray absorption edges might give new insights into complex materials.