The cocrystal of 2,4,6,8,10,12‐hexanitrohexaazaisowurtzitane (HNIW) with 2,4,6‐trinitrotoluene (TNT) (in a 1 : 1 mole ratio) was prepared by a solvent /non‐solvent (acetonitrile/distilled water) method, and systematically characterized by several methods. The thermal decomposition kinetics of HNIW ⋅ TNT cocrystal were investigated using dynamic Differential Scanning Calorimetry (DSC), and the apparent activation energy (Ea
) was calculated by Kissinger‐Akahira‐Sunose (KAS), Flynn‐Wall‐Ozawa (FWO) and Starink methods. The standard molar enthalpy of formation (ΔnormalfHmθ
) of HNIW ⋅ TNT cocrystal was acquired by a DC08‐1 Calvet microcalorimeter with the help of a rational thermochemical cycle and was 324.45±0.15 kJ mol−1. A continuous Cp mode of Micro‐DSC III was used to determine the specific heat capacity (Cp,m) of HNIW ⋅ TNT cocrystal from T=(283.15–333.15) K, and the Cp,m was 673.62 J mol−1 K−1 at 298.15 K.