Per- and polyfluoroalkyl substances (PFAS) have concerned the public due to their worldwide distribution and the threat they pose to drinking water safety and human health. Temperature and DC field-induced electroosmotic flow (EOF) are powerful tools to regulate organic contaminant adsorption and control PFOS (as a typical PFAS) transport in porous media. However, the co-driven mechanisms of temperature−electrokinetic transport of contaminants are still unclear. Here, we investigated the synergistic mechanisms of temperature−electrokinetic co-driven PFOS adsorption on zeolite and activated carbon as model geo-adsorbents. We found that DC fields increased PFOS adsorption on activated carbon by up to 19.8%, while they decreased PFOS adsorption on zeolite by up to 21.4%. Increasing the temperature decreased the adsorption of PFOS by activated carbon and zeolite. The temperature and electrokinetic synergistically drive EOF velocity to control PFOS adsorption. Synergistic mechanisms of temperature−electrokinetic regulated kinetic and temperature-regulated thermodynamic (the Gibbs free energy change ΔG) and kinetic (liquid viscosity) under various temperatures and DC field situations were analyzed with models. A kinetic approach interlinking viscosity, EOF velocity, and the kinetic adsorption constants was established to interpret the synergistic mechanisms which can be further adopted to estimate temperature−electrokinetic induced PFOS adsorption benefits to mineral and carbonaceous adsorbents. We concluded that such kinetic regulation may provide support for controlling the transmission of PFOS.