In situ/operando Mössbauer spectroscopy is one of the most powerful techniques to quantitatively monitor the coordination and electronic structure of Mössbauer isotopes (¹¹⁹Sn, ⁵⁷Fe, etc.) contained in heterogeneous catalysts under practical reaction conditions. To promote further progress in identifying the real structure of catalytic site(s) and revealing the underlying catalytic mechanism, herein we thoroughly summarize the recent advances of in situ/operando Mössbauer technique for probing heterogeneous catalysts and electrode materials for sustainable energy applications, including electrocatalysis, thermocatalysis, Li-ion batteries, etc. The unique role of this technique in different catalytic system is discussed with emphasis placed on several typical research advances. Moreover, the recent emerging operando Mössbauer technique for the study of single-atom catalysts, which is considered as a new eye for providing electronic-level insight into catalytic mechanism, is highlighted. Finally, the outlooks and challenges are discussed toward further application and rising influence of in situ/operando Mössbauer spectroscopy in heterogeneous catalysis.

原位/操作穆斯堡尔光谱是在实际反应条件下定量监测多相催化剂中穆斯堡尔同位素（¹¹⁹ Sn、⁵⁷ Fe 等）的配位和电子结构的最强大技术之一。为了促进在识别催化位点的真实结构和揭示潜在催化机制方面的进一步进展，我们在此全面总结了原位/操作数的最新进展穆斯堡尔技术用于探测可持续能源应用的多相催化剂和电极材料，包括电催化、热催化、锂离子电池等。讨论了该技术在不同催化系统中的独特作用，重点介绍了几个典型的研究进展。此外，强调了最近出现的用于研究单原子催化剂的操作穆斯堡尔技术，该技术被认为是提供对催化机制的电子级洞察的新视角。最后，讨论了原位/操作穆斯堡尔光谱在多相催化中的进一步应用和日益增长的影响的前景和挑战。