With the increasing global emphasis on green energy and sustainable development goals, the electrocatalytic oxygen evolution reaction (OER) is gradually becoming a crucial focus in research on water oxidation for hydrogen generation. However, its complicated reaction processes associated with its high energy barrier severely limit the efficiency of energy conversion. Recently, layered double hydroxide (LDH) has been considered as one of the most promising catalysts in alkaline media. Nonetheless, lacking a deep insight into the kinetic process of the electrocatalytic OER process is detrimental to the further optimization of LDH catalysts. Therefore, monitoring the catalytic reaction kinetic process via surface-sensitive in situ spectroscopy is especially important. In particular, the in situ Raman technique is capable of providing fingerprint information for surface species and intermediates in the operating environment. From the perspective of Raman spectroscopy, this paper provides an exhaustive overview of research progress in in situ Raman for the characterization of the catalytic mechanism of LDH catalysts, providing theoretical guidance for designing LDH materials. Finally, we present an incisive discussion on the challenges of the electrocatalytic in situ Raman technique and its future development trend.