An amphiphilic platinum NCN-pincer complex bearing hydrophilic tri(ethylene glycol) and hydrophobic dodecyl chains was designed and synthesized for use as a new aquacatalytic system. The complex self-assembled in an aqueous medium to form bilayer vesicles that catalyzed the hydrosilylation of alkenes by dimethyl(phenyl) silane in water to give the hydrosilylated products in good yields. In contrast, the complex in its amorphous form did not promote the reaction efficiently, and thus, the formation of a vesicular structure was essential to promote the reaction.