The oxygen-evolution reaction (OER) is an indispensable component of various energy storage and conversion electrocatalytic systems. However, the slow reaction kinetics have forced the development of advanced, efficient, and inexpensive OER electrocatalysts to break through the bottleneck of its application. Recently, the structural reconstruction of precatalysts has provided a promising avenue to boost the catalytic activity of electrocatalysts. Structural reconstruction implies atomic rearrangement and composition change of the pristine catalytic materials, which is a very complex process. Therefore, it is very crucial to have a deep understanding of the reconstruction chemical process and then modulate the reconstruction by deliberate design of electrochemical conditions and precatalysts. However, a systematic review of the structural reconstruction process, research methods, influencing factors and structure-performance relationship remains elusive, significantly impeding the further developments of efficient electrocatalysts based on structural reconstruction chemistry. This critical review is dedicated to providing a deep insight into the structural reconstruction during alkaline water oxidation, comprehensively summarizing the basic research methods to understand the structural evolution process and various factors affecting the structural reconstruction process, and providing a reference and basis for regulating the dynamic reconstruction. Moreover, the impact of reconstruction on the structure and performance is also covered. Finally, challenges and perspectives for the future study on structural reconstruction are discussed. This review will offer future guidelines for the rational development of state-of-the-art OER electrocatalysts.