A nanoscale thermal analysis on a polycrystalline energetic material, pentaerythritol tetranitrate (PETN), was performed using a heated atomic force microscope cantilever tip. Energetic materials are those materials that exhibit a release of stored chemical energy as thermal and mechanical energies. Both the heating and thermometry occurred in the solid-sate resistors at the base of the cantilever tips. Local thermal decomposition with a heated probe tip provided a unique method of controlling both the side and spatial resolution of voids in energetic materials. It is possible to measure thermophysical properties of a material surface by measuring both heat flow and temperature. The ability to manipulate the micro/nanostructure of polycrystalline materials could be used to study properties such as diffusion rates, phase transitions, and perform lithography in a wide variety of nanomaterials.