Nine per- and polyfluoroalkyl substances (PFASs), including six perfluoroalkyl carboxylic acids (PFCAs) and three perfluoroalkyl sulfonic acids (PFSAs), were tested to find their adsorption selectivity from surface water and the feasibility of the powder activated carbon (PAC) process between the perchlorination and coagulation processes by operating parameters such as mixing intensity, dosage, contact time, initial pH, and concentration of perchlorination. The removal efficiency of four types of PAC revealed that the coal-based activated carbon was clearly advanced for all of the PFASs, and the thermal regenerated PAC did not exhibit a significant reduction in adsorption capacity. The longer carbon chain or the higher molecular weight (MW) obtained a higher adsorption capacity and the MW exhibited a more proportional relationship with the removal efficiency than the carbon chain number, regardless of the PFCA and PFSA species. Approximately 80% and 90% equilibria were accomplished within 60 and 120 min for the long chain carbon PFAS, respectively, while for the short chain PFAS, 240 min was required to reach 85% equilibrium. The effect of mixing intensity (rpm) was not considered for the removal of the PFAS, although it was relatively influenced in the short PFAS species. Due to the surface charge of the PAC and the properties of protonation of the PFASs, the acid condition increased the PFASs’ adsorption capacity. The prechlorination decreased the removal efficiency, and the reduction rate was more significantly influenced for the short chain PFAS than for the long chain PFAS.