Three different methodologies have been evaluated to estimate the octanol-water partition coefficient (P-ow) of amphiphilic dithiocarbamates (DTC) (sodium salts of dithiocarbamic acids) with different substituents. The conventional shake-flask method has been used to measure P-ow coefficients. This method gave good results for dithiocarbamates with short aliphatic substituents, but it presents difficulties for measuring P-ow of DTC with long-chain substituents. The fragment contribution method PROLOGP, which uses theoretical calculations, has the advantage of its speed but it is unable to distinguish between isomeric compounds. Indirect methods show some advantages for screening purposes. This is the case of chromatographic and electrophoretic methods. Preliminary HPLC experiments showed that it was not useful for the determination of P-ow for DTC. So, micellar electrokinetic capillary chromatography (MECC) was used to estimate P-ow. Two different micellar systems, sodium dodecyl sulphate (SDS) and sodium deoxycholate (NaDCh) were tested. NaDCh was the most suitable surfactant for the analysis of DTCs. Retention measurements, at the same experimental conditions, for some compounds with known P-ow values were used to describe the correlation between P-ow and the MECC capacity factor (k'). Results showed a linear relation, which allowed the estimation of the P-ow for dithiocarbamates. The obtained data were compared with the measured P-ow coefficients obtained by the conventional shake-flask method and those calculated with the fragment contribution method PROLOGP. (C) 2002 Elsevier Science B.V. All rights reserved.