Of the large number of emerging pollutants discharged from wastewaters into surface waters, surfactants are among those with the highest concentrations. However, few monitoring in river waters of these substances have already been performed and only on a few families, mostly anionic. This work aimed to develop a multi-family analytical strategy suitable for the quantification of low concentrations of surfactant in surface waters. Twelve families of surfactants, anionic, cationic and non-ionic were selected. Their quantification by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) and their extraction by SPE were optimized by comparing different retention mechanisms. The best performances were obtained with a C18 grafted silica LC column and a hydrophilic-lipophilic balanced (HLB) polymeric SPE cartridge. The final analytical method was validated and applied for the quantification of surfactants in 36 river water samples. Method limits of quantification (LQ), intra and inter days precision and trueness were evaluated. With LQ between 15 and 485 ng/L, and trueness over 80%, this method was suitable for monitoring surfactants in surface water. Application on French river water samples revealed the presence of anionic, cationic and non-ionic surfactants with median concentrations from 24 ng/L for octylphenol ethoxylates (OPEO), up to 4.6 μg/L regarding linear alkylbenzene sulfonates (LAS).