Temperature-induced reversible micelle–vesicle transition is achieved in aqueous solution of a single pseudogemini surfactant without any additive. The pseudogemini surfactant is constructed by tetradecyldimethylamine (DA14) and maleic acid (MA) at a 2 : 1 molar ratio of DA14/MA in aqueous solution via non-covalent bonds. The transition temperature can be adjusted by changing either the total surfactant concentration or the DA14/MA ratio. This reversible system, which has both low material costs and convenience, has potential applications in household and industry fields.