The thermal conductivity of explosives is an important index to understand the non-shock initiation and the non-ideal detonation. On the basis of experimental thermal conductivity data of polymers, two methods for calculating thermal conductivity, which are proposed by Bicerano and Askadskii, respectively, are compared. By calculating and comparing the relative deviations, Askadskiii group contribution method is verified to be efficient and thus adopted, because of its small relative deviation. Based on the analysis results of the structures, properties and thermal conduction mechanism of conjugated polymers, several energetic conjugated polymers are designed by adding energetic groups —NO₂, —N₃ and —ONO₂ up to the conjugated polymer structures. A coupling between phonon conduction and electron conduction in the conjugate systems of energetic conjugated polymers will lead to an increase in the thermal conductivity. Thermal conductivity calculation shows that the new designed conjugated energetic polymers exhibit the enhanced thermal conductivity, above 1.0 W·mK^-1