Conventionally, carbenium and onium ions are prepared in the presence of nucleophiles due to their instability and transient nature. The nucleophiles that are unstable or inert to the reaction media cannot be used for reaction with the cationic species to access the desired compounds. Developing methods for generating organic cations irreversibly in the absence of nucleophiles is essential to overcome these limitations. The "Cation Pool" method developed by Yoshida and co-workers stands out as a reliable strategy to generate and accumulate the reactive cations in solution in the absence of nucleophiles. The cation pool method involves the electrolysis of the substrate in the absence of nucleophiles, usually at low temperatures. Moreover, the generation of halogen and chalcogen cations through electrolysis needs extra care because of their low stability. The current thesis describes the development of the new protocol, unlike the conventional electrochemical redox process for the generation and accumulation of cation pools for halonium ions, methyl(methylene)sulfonium ions, chlorodimethylsulfonium ions and their application in organic synthesis.