The phase behaviors of dihydrogenated tallowalkyl dimethyl ammonium chloride (DHTDMAC), water and different hydrocarbons were studied. Addition of different hydrocarbons to DHTDMAC and water system formed rich aggregates, including two liquid crystal aggregates and water in oil microemulsion. The polarity of hydrocarbon affects stability and phase behavior of hydrocarbon–DHTDMAC–water. The polar hydrocarbons, cyclohexane and benzene stabilize the phase structure. Interaction of different hydrocarbon molecules with liquid crystal phase was studied by the small angle X-ray diffraction. The results indicate that the variable hydrocarbon and water fraction penetrate into surfactant association structure with the different hydrocarbons, which affects the stability and Kraft point of surfactant aggregates. Less water penetrates into lamellar liquid crystal where more oil penetrates into the same area, which stabilizes the aggregate's phase structure.