The growing need for environmentally friendly energy solutions has spurred the creation of self-supporting two-dimensional electrocatalysts, which provide improved durability, a high surface area, and adjustable electronic characteristics. This chapter presents a comprehensive review of their synthesis methods, structural diversity, and performance optimization strategies. It begins by categorizing key 2D electrocatalysts, including transition metal dichalcogenides (TMDs), MXenes, layered double hydroxides (LDHs), hybrid structures, and metal-free catalysts, highlighting their distinct physicochemical properties and catalytic activity. The discussion then shifts to the role of different substrate types—metal, carbon-based, transparent conductive, and non-conductive—in influencing electrocatalytic performance and long-term stability. A systematic analysis of advanced fabrication techniques follows, covering electrodeposition, solution-based synthesis (SILAR, gas–liquid interface methods, and spin coating), solvothermal approaches, and vapor deposition techniques (CVD and PVD), with an emphasis on their advantages, limitations, and applications in hydrogen evolution and electrochemical energy conversion. By integrating recent advances in material design and synthesis, this chapter underscores the growing significance of self-supported 2D electrocatalysts in next-generation energy technologies and lays the groundwork for developing scalable and high-performance electrocatalysts.