AbstractAmmonium dinitramide (ADN) has been considered the potential substitute for ammonium perchlorate in solid green propellants. However, it has also some drawbacks due to its high hygroscopicity and chemical incompatibility with some of the components present in composite propellant formulations. On the other hand, ADN melts at temperatures below degradation, which makes emulsion crystallization an important method to prepare spherical ADN particles that benefit both propellant slurry processing and casting. Spherical ADN particles were prepared by emulsion crystallization to be used for the microencapsulation studies, and whose method was assessed to better understand which parameters may affect the ADN particles formation. Microencapsulation protects ADN particles as it addresses hygroscopicity besides the given protection from chemical incompatibility. Polyurethane made of hydroxyl‐terminated polybutadiene was selected as a coating material because of its common use in propellants as a binder. Also, the good performance of methylene diphenyl diisocyanate as a curing agent was such that it was used in the whole study. The number of layers and the processing time played important roles in the formation of the capsule as seen in the impermeability tests. Besides, drying at 50 °C for 168 h showed to be even more beneficial on average for the capsule protective property. Chemical compatibility between the capsule and ADN was confirmed at 60 °C which allows it to be used as a protective coating. However, the obtained average coating thickness of ten microns has to be reduced yet with more efficient protective coating materials.