Ultrathin nanosheets possess a distinctive structure characterized by an abundance of active sites fully accessible on their surface. Concurrently, their nanoscale thickness confers an extraordinarily high specific surface area and promising electronic properties. To date, numerous strategies have been devised for synthesizing precious metal nanosheets that exhibit excellent electrocatalytic performance. In this paper, recent progress in the controlled synthesis of two-dimensional, ultrathin nanosheets by a self-assembly mechanism using functional surfactants is reviewed. The aim is to highlight the key role of functional surfactants in the assembly and synthesis of two-dimensional ultrathin nanosheets, as well as to discuss in depth how to enhance their electrochemical properties, thereby expanding their potential applications in catalysis. We provide a detailed exploration of the mechanisms employed by several long-carbon chain surfactants commonly used in the synthesis of nanosheets. These surfactants exhibit robust electrostatic and hydrophobic effects, effectively confining the crystalline growth of metals along lamellar micelles. Moreover, we present an overview of the electrocatalytic performance demonstrated by the ultrathin nanosheets synthesized through this innovative pathway. Furthermore, it offers valuable insights that may pave the way for further exploration of more functional long-chain surfactants, leading to the synthesis of ultrathin nanosheets with significantly enhanced electrocatalytic performance.