An efficient and highly selective combined cation exchange-liquid-liquid extraction method coupled with GC-MS determination is proposed for the separation and concentration of 4-nonylphenol from various water matrices. The method has good precision expressed as repeatability: mean value 97.28% with a RSD value of 4.20%. Recovery of alkylphenols from spiked samples varies from 92 to 101% and the values obtained are higher than with other methods currently in use. The method was successfully applied for the determination of 4-nonylphenol from various water matrices.