The electrocatalytic reduction of carbon dioxide into organic fuels and feedstocks is a fascinating method to implement the sustainable carbon cycle. Thus, a rational design of advanced electrocatalysts and a deep understanding of reaction mechanisms are crucial for the complex reactions of carbon dioxide reduction with multiple electron transfer. In situ and operando techniques with real-time monitoring are important to obtain deep insight into the electrocatalytic reaction to reveal the dynamic evolution of electrocatalysts’ structure and composition under experimental conditions. In this paper, the reaction pathways for the CO reduction reaction (CORR) in the generation of various products (e.g., C and C) via the proposed mechanisms are introduced. Moreover, recent advances in the development and applications of in situ and operando characterization techniques, from the basic working principles and in situ cell structure to detailed applications are discussed. Suggestions and future directions of in situ/operando analysis are also addressed.