Surfactants have attracted great attention in a wide range of potential applications such as nano-building blocks or drug delivery. However, the morphology of an aggregate formed from the surfactant in a fairly low concentration including below the critical micelle concentration (CMC), which is key information to easily control the morphology of surfactant aggregates at various concentrations, has not been exploited yet. Herein we report a thermally responsive and spontaneous surfactant vesicle by mixing a cationic surfactant and an organic derivative below as well as above the CMC of the surfactant. Depending on the concentration of the additive organic derivative and temperature, the spontaneous surfactant vesicles are easily transformed into the micelle or isotropic free surfactant phase. Furthermore, the vesicle to cylindrical micelle transition temperature of the prepared surfactant vesicle could be easily controlled by the concentration of the additive organic derivative that provides the thermally responsive surfactant vesicles with a variety of transition temperatures, allowing the surfactant vesicle to be used in gene or drug delivery.