Composite solid propellants have used cast molding production technology for many decades, with intrinsic limitations on production flexibility, promptness, and grain geometry, as well as environmental implications on toxicity and global carbon footprint. This traditional method involves the use of toxic chemicals, has a long processing time, requires high temperature, and the products have limited geometries. To overcome those issues, different photo-curable resins have been evaluated as possible matrices. In fact, the UV-curing process is fast and has low energy consumption. The photocuring reaction parameters of six different pristine formulations were evaluated by Fourier transform infrared spectroscopy analysis. After finding the optimal curing parameters, different composites were prepared by adding 75 or 80 wt% ammonium sulfate particles used as an inert replacement for the oxidant. The thermomechanical properties and thermal resistance of the UV-cured composites were characterized via dynamic thermal-mechanical and thermogravimetric analysis. Subsequently, the mechanical properties of the inert propellants were investigated by tensile tests. The most promising resin systems for the production of solid rocket propellants were then 3D printed by an in-house developed illumination system and the obtained object micro-structure was evaluated by X-ray computed tomography.