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We report a selective, sensitive and fast liquid chromatography/tandem mass spectrometry (LC/MS/MS) method for the determination of diallyldimethylammonium chloride (DADMAC) in water. Hydrophilic interaction liquid chromatography (HILIC) was used to avoid ion-pairing reagents, which are generally employed to retain cationic compounds. The complementary information obtained in a triple quadrupole mass spectrometer and in an ion trap Orbitrap has been used to study the fragmentation of the DADMAC cation [M](+) and for the correct assignment of the products ions. The HILIC/MS/MS method developed, using electrospray ionization in positive ion mode and selected reaction monitoring (SRM) acquisition mode, led to a reliable determination and confirmation of the DADMAC cation in water samples down to 50 ng L(-1). The low detection limit achieved, in combination with the absence of matrix effects, allowed the direct analysis of samples without any pretreatment, preconcentration or clean-up step. DADMAC was determined in samples collected in a drinking water treatment plant (DWTP) in Barcelona (Spain) and it was found in the influent at the µg L(-1) level.