In the present work we have performed a controlled study of nitrocellulose (up to 13% nitrogen content) at high pressure and elevated temperature aimed at understanding the chemical decomposition process in this material under relatively slow kinetic conditions. We have found that during the course of thermal decomposition a highly conducting species is developed. This is presumably a consequence of the scission of covalent bonds and breaking-up of long polymeric chains favoring a high molar concentration of short diradical chain fragments with a strong concentration of unsatisfied valence spins or dangling bonds. We have also observed a minimum resistance turning point subsequent to the range of increasing conductivity which appears to be associated with a bond reconstruction process that develops a black carbonaceous end product.