Phase inversion of aqueous two-phase systems with excess cationic surfactant (abbreviated as ATPS-C) formed by aqueous mixtures of 1,3-propanediyl bis(dodecyl dimethylammonium bromide) (abbreviated as 12-3-12) and sodium dodecyl sulfonate (abbreviated as AS) at 318.15 K was investigated. The experimental results indicate that addition of NaF, NaCl, NaHCO3, or NaNO3 can result in phase inversion of ATPS-C formed by 12-3-12/AS systems; however, addition of NaBr cannot lead to phase inversion. TEM micrographic experiments illustrate that there is no direct relationship between the microstructures of the concentrated phase in ATPS-C and phase inversion. To interpret the phase-inversion phenomena of ATPS-C, the phase composition, phase density, and phase volume ratio between the dilute phase and the concentrated phase in ATPS-C were investigated. Phase composition analysis results illustrate that for the ATPS-C formed by 0.10 mol.kg(-1) 12-3-12/AS mixed system, the concentration of Br- counterions in the dilute phase of ATPS-C increases with addition of NaF, NaCl, NaHCO3, or NaNO3. At the same time, the molar ratio between the F- (Cl-, HCO3-, or NO3-) counterions and Br- counterions in the concentrated phase of ATPS-C increases also. It illustrates that part of the bromide counterions which are the natural counterions of the surfactant 12-3-12 in excess are exchanged by other anionic counterions when an additional salt is added to the system. The investigation indicates that the common ground of the added F-, Cl-, HCO3 or NO3- counterions is that they all make a smaller density contribution than that of Br- counterions, although they have a weaker or stronger counterion binding ability with the mixed positively charged aggregates in ATPS-C than that of Br- counterion. Density experiments illustrate that the density increase of the dilute phase is larger than that of the concentrated phase in the ATPS-C with addition of NaF, NaCl, NaHCO3, or NaNO3; thus, phase inversion occurs. The densities of the added inorganic sodium salt aqueous solution and the order of the Hofmeister series for the added inorganic anions with respect to the chaotropic headgroup of 12-3-12 play important roles in the phase inversion of ATPS-C.