The thermal behavior of 2,3-dimethyl-2,3-dinitrobutane (DMNB), a detection agent for explosives, was studied using various thermoanalytical techniques. Vapor pressure data for DMNB were obtained from differential scanning calorimetry (DSC) measurements. The enthalpy of sublimation for DMNB over different temperature ranges was estimated using DSC and dynamic and isothermal thermogravimetry (TG). Kinetic parameters for the decomposition of neat DMNB and DMNB in mesitylene, solution were determined using various methods, and there was reasonable agreement between the results obtained for the solid and solution. Additionally, DSC and accelerating rate calorimetry (ARC) results at super-ambient pressures were compared to earlier heat flow calorimetry (HFC) results, and the effect of pressure on the thermal behavior of DMNB is also discussed.