Recently photocatalytic treatment of municipal reverse osmosis concentrate (ROC) has drawn increasing attention due to its relatively high efficiency and low cost. However, photocatalytic reactions by commercially available TiO₂ are not able to degrade fluorosurfactants in the ROC sample due to the absence of photoreactive groups in these compounds. Here we investigated adsorption and coagulation methods and their efficiencies in removing fluorosurfactants. The analysis and characterization methods included mass spectrometry (LC-QToF), total organic carbon (TOC), fluorescence & UV–Visible spectra, SEM, IR, N2 sorption, zeta potential, and elemental analysis. Ferric chloride (FER) coagulation was found to be quite efficient in removing fluorosurfactants, while powdered activated carbon (PAC) adsorption was inefficient. The FER pre-treatment process was found to perform better than the post-treatment process in removing the fluorosurfactants. FER selectively removed the bulky fluorosurfactants with long branches but not the slim ones with short or no branches. At a concentration of 10.60 mM, FER could efficiently remove 62.19% fluorosurfactants in total from the ROC sample. The applicability of Freundlich and Langmuir models for the adsorption processes was also investigated. FER was able to remove fluorosurfactant while PAC unable. While the PAC removal mechanism was adsorption, the FER coagulation mechanism was far more complicated.