Nano- and submicron-sized crystals are too small to contain inclusions and are, therefore, expected to have a higher internal quality compared to conventionally sized particles (several tens to hundreds of microns). Using electrospray crystallization, nano- and submicron-sized crystals can be easily produced. With the aid of electrospray crystallization, a mist of ultrafine solution droplets is generated and subsequent solvent evaporation leads to crystallization of submicron-sized crystals. Using cyclotrimethylene trinitramine (RDX) solutions in acetone, the conditions for a stable and continuous jet were established. At relatively small nozzle diameters and relatively low potential differences, hollow spheres of RDX crystals were observed. At a higher nozzle diameter and potential difference and in the region of a continuous jet, RDX crystals with an average size of around 400 nm could be produced. In order to test the quality of the submicron-sized energetic material, impact and friction sensitivity tests were carried out. The test results indicate that the submicron-sized product had reduced friction sensitivity, indicating a higher internal quality of the crystalline product.