For the motion control of individual molecules at room temperature, optical tweezers could be one of the best approaches to realize desirable selectivity with high resolution in time and space. Because of physical limitations due to the thermal fluctuation, optical manipulation of small molecules at room temperature is still a challenging subject. The difficulty of the manipulation also emerged from the variation of molecular polarizability depending on the choice of molecules as well as the molecular orientation to the optical field. In this article, we have demonstrated plasmonic optical trapping of small size molecules with less than 1 nm at the gap of a single metal nanodimer immersed in an electrolyte solution. In situ electrochemical surface-enhanced Raman scattering measurements prove that a plasmonic structure under electrochemical potential control realizes not only the selective molecular condensation but also the formation of unique mixed molecular phases which is distinct from those under a thermodynamic equilibrium. Through detailed analyses of optical trapping behavior, we established the methodology of plasmonic optical trapping to create the novel adsorption isotherm under applying an optical force at electrified interfaces.