摘要： As one of the most remarkable oxygen evolution reaction (OER) electrocatalysts, metal chalcogenides have been intensively reported due to their high OER activities during the past few decades. It has been reported that electron-chemical conversion of metal chalcogenides into oxides/hydroxides would take place after OER. However, the transition mechanism of such unstable structures, as well as the real active sites and catalytic activity during OER for these electrocatalysts, has not been understood yet, which urgently needs a direct observation for the electrocatalytic water oxidation process, especially at nano or even angstrom scale. In this research, by employing advanced Cs-corrected transmission electron microscopy (TEM), a step by step oxidational evolution of amorphous electrocatalyst CoSx into crystallized CoOOH in OER has been in situ captured: irreversible conversion of CoSx to crystallized CoOOH is initiated on the surface of electrocatalysts with a morphology change via Co(OH)2 intermediate during OER measurement, where CoOOH is confirmed as the real active species. Besides, this transition process has also been confirmed by multiple applications of X-ray photoelectron spectroscopy (XPS), in situ Fourier-transform infrared spectroscopy (FTIR) and other ex situ technologies. Moreover, based on this discovery, a high-efficiency electrocatalyst of a nitrogen-doped graphene foam (NGF) coated by CoSx has been explored through a thorough structure transformation of CoOOH. We believe this in situ and in-depth observation of structural evolution in OER measurement can provide insights into the fundamental understanding of the mechanism for OER catalysts, thus enabling the more rational design of low-cost and high-efficient electrocatalysts for water splitting.