In this review, after a brief description of the underlying principles of x-ray absorption spectroscopy, we describe the results that enable one to obtain fundamental new insights into the rich physics and chemistry of chalcogenides. We start with chalcogenide glasses taking the readers from the structure of amorphous selenium and confined single Se chains and carry on to photo-induced structural changes. We subsequently describe application of EXAFS to monolayers of transition-metal dichalcogenides. The review is concluded by the results that were seminal to understand the phase-transition mechanism in so-called phase-change alloys that are widely used in optical and non-volatile memory devices. We place special accent on the conclusions that were only possible to draw based on the local nature of x-ray absorption spectroscopy.
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