The short-chain n-alcohol-induced changes in phase behaviors of aqueous mixed 1,3-propanediyl bis(dodecyl dimethylammonium bromide) (12-3-12) and sodium dodecyl sulfonate (AS) system have been investigated. For the 12-3-12/AS/H2O mixed system, there are two kinds of aqueous two-phase systems with excess cationic surfactant (ATPS-C). The molar ratio of 12-3-12 to AS (MR12-3-12/AS) and the total surfactant concentration (m(T)) in the top phase are smaller than those in the bottom phase of ATPS-C. It is worth noting that the addition of ethanol or n-propanol leads to different influences on the ATPS-C. Molecular dynamics (MD) simulation results illustrate that the different influences ascribe to the difference in the cosurfactant effect of ethanol and n-propanol. When ethanol is used as additive, the difference in m(T) leads to the difference in interactions between surfactants and ethanol for the two coexisting phases of ATPS-C, determining the difference in their combination ability with the mixed solvent. It is the main reason for the ethanol-induced phase inversion of the first kind of ATPS-C. When n-propanol is added, in addition to m(T), MR12-3-12/AS is also a key factor influencing the interactions between 12-3-12 and AS and between surfactants and n-propanol due to the stronger cosurfactant effect of n-propanol. MD simulations indicate that vesicles with smaller MR12-3-12/AS are easier and faster to form. These vesicles spontaneously accumulate at the top phase accompanied by certain amount of mixed solvent transferred from the bottom phase of ATPS-C. Meanwhile, the competition for the mixed solvent arising from the surfactant-rich bottom phase prevents the transferring. The two factors work together to cause the increase of m(T) in the top phase of ATPS-C with the addition of n-propanol, leading to n-propanol-induced phase concentration inversion rather than phase inversion of ATPS-C. On the basis of the experimental results and MD simulations, ethanol-induced phase inversion mechanism or n-propanol-induced phase concentration inversion mechanism of ATPS-C has been proposed.