As a highly effective welding method, PPCA-TIG (Powder Pool Coupled Activating Flux–Tungsten Inert Gas) welding aims to achieve automated activation of TIG welding through the use of suitable activating fluxes. However, due to the unique transitional behavior of activating elements, the mechanism of PPCA-TIG is a little bit different from common activating TIG welding. In this research, a two-dimensional model is established to investigate the effect of four activating fluxes (TiO2, SiO2, MnO2, CaF2) on arc morphology and force. A series of welding experiments is performed to study the impact of the different activating elements on the molten pool. The results show that the increase in the penetration of TiO2 is related to the high arc temperature and great arc force and electromagnetic force in the molten pool. The problem of the softening of 3003 aluminum alloy welded joints is solved. Other activating fluxes are less effective than TiO2. The addition of calcium fluoride significantly affects penetration. The use of TiO2, SiO2 and MnO2 changes the molten pool viscosity and affects the molten pool oscillation, thus affecting the weld quality.