Twenty chiral pesticides were tested, of which seven samples were directly separated by HPLC using cellulose tris-3,5-dimethyl carbamate (CDMPC) chiral stationary phase under RP conditions. The influence of mobile phase composition and column temperatures from 0°C to 40°C on the separations were investigated. The mobile phases were methanol/water or ACN/water at a flow rate of 0.8 mL/min with UV detection at 230 or 210 nm. Epoxiconazole, terallethrin, benalaxyl, and diclofop-methyl were observed to obtain the baseline separation under suitable conditions and other pesticides pyriproxyfen, lactofen, and quizalofop-ethyl were separated partially. The retention factors (k) and selectivity factor (α) for the enantiomers of most investigated pesticides decreased upon increasing the temperature except for the selectivity factors (α) of pyriproxyfen in methanol/water. The ln α–1/T plots for racemic chiral pesticides were linear at the range of 0–40 except for that of pyriproxyfen enantiomers in methanol/water and the chiral separations were controlled by enthalpy. Better separations were not always at low temperature. The elution orders of the eluting enantiomers were determined by a circular dichroism (CD) detector.