Summary. This study reports the effect of a nonionic perfluorinated surfactant, N-polyoxyethylene-N-propyl perfluorooctane sulfonamide (PFOSA), as additive of background electrolyte on capillary electrophoresis (CE) of common inorganic cations. The association constants (K ass ) for PFOSA estimated from the electrophoretic mobility of analyte cations were the order of Mg 2+ > Ca 2+ > Sr 2+ >> K + ≈ NH 4 + > Na + ≈ Li + . The K ass values were larger than those for zwitterionic and nonionic surfactants with hydrocarbon moiety. Use of PFOSA made another essential contribution to the determination of inorganic cations in a protein-containing sample. This was considered because high solubility of PFOSA for proteins functioned as suppressor for protein adsorption to the capillary wall. Four inorganic cations, Na + , K + , Mg 2+ , and Ca 2+ , in human saliva sample were successfully determined by sample injection without any pretreatments except for filtration and dilution.