Aerofloats, such as aniline aerofloat ((C6H5NH)2PSSH), are extensively employed for collection activities particularly in cases where minerals are in flotation. Although these aniline aerofloat has efficient collection properties, they are ordinarily biologically persistent chemicals in which case their residual, as well as their byproducts, might pose great environmental risks to water and soils. In this study, the removal efficiency of aniline aerofloat (AAF) by a combination of vacuum ultraviolet (VUV) and ozone (O3) process (VUV/O3) was evaluated. Furthermore, the impacts of pH, O3, the concentration of AAF and coexisting ions (SiO32−, CO32−, Cl− (Na+), SO42−, Ca2+) were systematically studied. The experiments revealed that, with initial AAF of 15 mg/L, AAF removal >88% was feasible within reaction time of 60 min, pH of 8 and O3 of 6 g/h. The order of influence of the selected coexisting ions on the degradation of AAF by VUV/O3 is Ca2+ > CO32− > SiO32− > Cl− (Na+) >SO42−. Compared with VUV and O3 in terms of pollutant degradation rate, VUV/O3 manifested a remarkable performance followed by O3 and VUV processes. Additionally, the degradation kinetics of AAF by the VUV/O3 process agreed well with first-order elimination kinetics.