Controlling the synthesis of metal nanostructures is one approach for catalyst engineering and performance optimization in electrocatalysis. As an emerging class of unconventional electrocatalysts, two-dimensional (2D) metallene electrocatalysts with ultrathin sheet-like morphology have gained ever-growing attention and exhibited superior performance in electrocatalysis owing to their distinctive properties originating from structural anisotropy, rich surface chemistry, and efficient mass diffusion capability. Many significant advances in synthetic methods and electrocatalytic applications for 2D metallenes have been obtained in recent years. Therefore, an in-depth review summarizing the progress in developing 2D metallenes for electrochemical applications is highly needed. Unlike most reported reviews on the 2D metallenes, this review starts by introducing the preparation of 2D metallenes based on the classification of the metals (e.g., noble metals, and non-noble metals) instead of synthetic methods. Some typical strategies for preparing each kind of metal are enumerated in detail. Then, the utilization of 2D metallenes in electrocatalytic applications, especially in the electrocatalytic conversion reactions, including the hydrogen evolution reaction, oxygen evolution reaction, oxygen reduction reaction, fuel oxidation reaction, CO reduction reaction, and N reduction reaction, are comprehensively discussed. Finally, current challenges and opportunities for future research on metallenes in electrochemical energy conversion are proposed.