From the experimental n-octanol/water partition coefficients (log Poct) of 33 1,2-dithiole-3-thiones and 18 1,2-dithiol-3-ones and their respective log k, Collander-type relationships were established at various volume fractions of methanol in the mobile phase and on an ODS 2 stationary phase. Collander-type relationships were also established between log Poct and log K0 (capacity factor extrapolated to 0% of organic modifier). The correlations are good, and their parameters depend on the volume fraction of organic modifier, as expected. These relationships were used to evaluate the log Poct of seven very lipophilic dithiolethiones (3.7 < log P < 7.2). Extrapolated values were compared with calculated values from fragmental constants determined in a previous work and with those given by Rekker.