CO₂-responsive smart fluids have been widely investigated in the past decade. In this article, we reported a CO₂-responsive smart fluid based on supramolecular assembly structures varying from vesicles to wormlike micelles. Firstly, oleic acid and 3-dimethylaminopropylamine reacted to form a single-chain weak cationic surfactant with a tertiary amine head group, N-[3-(dimethylamino)propyl]oleamide (NDPO). Then, 1,3-dibromopropane was used as the spacer to react with NDPO to form a gemini cationic surfactant, trimethylene α,ω-bis(oleate amide propyl dimethyl ammonium bromide) (GCS). By controlling the feed ratio of 1,3-dibromopropane and NDPO, we found that the mixtures of GCS and NDPO with the molar ratio of 7 : 3 approximately could form vesicles in aqueous solution by supramolecular self-assembly. After bubbling CO₂, the tertiary amine of NDPO was protonated. The packing parameter of the mixed surfactants reduced accordingly, accompanied by the transition of aggregates from vesicles to wormlike micelles. As a result, the zero-shear viscosity of the solution increased by more than four orders in magnitude. When the solid content of GCS/NPDO mixtures was higher than 5 wt% in solution, the sample treated by CO₂ behaved as a gel over a wide frequency range with shear-thinning and self-healing properties. In addition, the sol–gel transition could be repeatedly and reversibly switched by cyclically bubbling CO₂ and N₂. Our effort may provide a new strategy for the design of CO₂-responsive smart fluids, fostering their use in a range of applications such as in enhanced oil recovery.