A simple and rapid HPLC method has been developed using a polysaccharide chiral stationary phase (Chiralpak AD-H) for the resolution of glycidyl tosylate enantiomers. These compounds were obtained by asymmetric epoxidation of allyl alcohol with chiral titanium-tartrate complexes as catalyst after in situ derivatization of the intermediate glycidols. Separations were achieved using two types of mobile phase: a normal-phase (n-hexane), and a polar-phase (methanol or acetonitrile). The influence of the type and concentration of organic modifier in the mobile phase (ethanol or 2-propanol), the flow rate and the column temperature was investigated. In normal-phase mode, the optimized conditions were: n-hexane/ethanol 70/30 (v/v) at a flow rate of 1.2 mLmin(-1) and 40 degrees C. In polar-phase mode, the optimized conditions were: methanol at a flow rate of 0.8 mLmin(-1) and 20 degrees C. In both cases, analysis time was </=11 min and the chiral resolution was >/=2. Nevertheless, due to the better Rs obtained in normal-phase mode, only this method was validated to avoid peaks overlapping in real samples. This method was found to be linear in the 5-300 microgmL(-1) range (R(2)>0.999) with an LOD of 1.5 microgmL(-1) for both glycidyl tosylate enantiomers. Repeatability and intermediate precision at three different concentrations levels were below 0.5 and 7.2% R.S.D. for retention time and area, respectively. This method was applied successfully for the determination of glycidyl tosylate enantiomers after in situ derivatization of glycidols obtained in allylic alcohol asymmetric epoxidation processes with chiral titanium-tartrate complexes as catalysts.