We report here the application of subcritical water in chiral separations on two popular polysaccharide chiral stationary phases (CSPs): Chiralpak AD and Chiralcel OD. The behavior of these two CSPs was studied under reversed phase conditions at room temperature to discover the maximum percentage of water in the mobile phase, which provided the separation of enantiomers of flavanone and benzoin, respectively, in a reasonable time (i.e., less than 1 h). Then, the stability of Chiralpak AD and Chiralcel OD versus temperature was investigated and discussed. Chiralcel OD separation of flavanone racemate was obtained at 120°C with water and 2-propanol (80/20) as the mobile phase, while benzoin racemate was separated in pure water at 160°C. Separations of several racemates were also presented, and advantages and limitations of the technique were discussed. Chirality, 2011. © 2011 Wiley Periodicals, Inc.