This paper aims to provide a practical catanionic vesicle-boosting method by means of cosolvent addition in water and to propose a theoretical explanation which can delineate the general trend of cosolvent effects and elucidate the possible role of cosolvent in the formation of catanionic vesicles. Effects of four homologous cosolvents (methanol, ethanol, 1-propanol, and 1-butanol) on the spontaneous formation of vesicles from eight 1:1 anionic-cationic mixed surfactant systems, sodium alkyl sulfates-alkyltrimethylammonium bromides (C(n)SO4Na-C(m)N(CH3)3Br; n = 12, 14; m = 8, 10, 12, 14), at a total surfactant concentration of 10 mM were systematically studied. The experimental results revealed that varied changes in vesicle formability of different mixed surfactant systems may result from various kinds and amounts of cosolvent. Four types of cosolvent effects, however, can be classified. Among them, cosolvent effects type 2 and type 3 would serve the purpose and were exemplified by C12SO4Na-C10N(CH3)3Br, C14SO4Na-C10N(CH3)3Br, and C12SO4Na-C12N(CH3)3Br mixed surfactants. Furthermore, the effectiveness of vesicle boosting increases in the order 1-butanol > 1-propanol > ethanol > methanol. An explanation of cosolvent effects based on the medium dielectric constant was then proposed.