A simple, sensitive LC-ESI-MS method was optimized for quantitative analysis of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) in environmental samples. Under negative ionization mode, HMX can form adduct ions with various organic acids and salts, including acetic acid, formic acid, propionic acid, ammonium nitrate, ammonium chloride, sodium nitrite, and sodium nitrate. Acetic acid was chosen as additive and the ion, [M+CH 3 COO] − with m/z=355 was used for selective ion monitoring (SIM) in this study. Good sensitivity was achieved with low acetic acid concentration in the mobile phase and relatively low capillary temperature. The method detection limit was 0.78pg for HMX in standard solution. Linearity (R 2 >0.9998) was obtained at low concentrations (0.5–50μg/L). This method has been used to determine HMX concentrations in water samples and lizard egg samples from an animal exposure study.