The thermal hazard of 2,4-dinitroanisole (2,4-DNAN) was evaluated by microcalorimetry methods. The specific heat capacity, melting enthalpy, and the solidification heat of 2,4-DNAN were determined with a Micro-DSCIII calorimeter. The thermal decomposition behavior of 2,4-DNAN at four different heating rates was studied by using a C-500 type calvet microcalorimeter. The kinetic and thermodynamic parameters were obtained from the analysis of the heat flow data. The critical temperature of thermal explosion (Tb) and the initial decomposition temperature (Tp0) were determined to distinctly evaluate the thermal hazard of 2,4-DNAN.