The occurrence of per- and polyfluoroalkyl substances (PFAS) was investigated inside two manufacturing facilities in China. Levels, profiles, and spatial distribution of the detected PFAS were found to be distinctly site-specific and influenced by the area's historic function, production structure of the plant, downpour-induced accidental pollution, and variations in the adsorption and transport of compounds. Very high concentrations of PFAS [mainly C4 and C8 perfluoroalkyl sulfonic acids (PFSAs)] were found in topsoil and groundwater from both plants, with the highest values of 4.89 × 10 6 μg/kg dw and 1.10 × 10 4 μg/L, respectively. Elevated concentrations of perfluoroalkyl carboxylic acids (PFCAs) in this study were attributed to their unintentional formation during the electrochemical fluorination process, which might be an overlooked source of PFCA. PFAS generally showed decreasing trends from shallow layers to the bottom of the soil core and demonstrated some downward migrations at different soil depths with time, and C4-C8 PFAS presented a deeper seepage than their long-chain homologues. Total organic carbon appeared to be more important for PFAS sorption to the topsoil than to the soil core. Workers were at potential risk of exposure to perfluorooctanesulfonic acid via soil at production and storage related sites. This study provides a critical reference for the systematic control of PFAS pollution around manufacturing facilities and a proof for an overlooked source of PFCA.