A selective and sensitive high performance liquid chromatography(HPLC) was optimized for quantitative analysis of pentaerythritol tetranitrate(PETN) based polymer bonder explosive (PBX) with conditions of SB-C18 column(4.5 mm×250 mm, 5 μm), UV detector, mobile phase V(acetonitrile):V(water)=70:30, flow rate of 1.0 mL·min^-1 and detection wavelength 225 nm. The influences of sample treat method, sample mass and solvent were studied. Results show that the relative standard deviation of reproducibility is 0.13% when PBX sample is cutted to granule (volume 1.0 mm³, mass 200 mg) in 100 mL flask and ultrarsonic dissolved 30 min by acetonitrile and then stands for 16 h. T he detection limit for PETN is 0.054 μg·mL^-1 and there is a good linear between the peak areas and the mass concentration of 0.8-2.0 mg·mL^-1 with linear correlation coefficients of 0.9994.