A morphologically stable silicon oil microcapsule base polystyrene as shell modified with TiO2 and Si3N4 nanoparticles was synthesized, characterized and applied as an inhibitor for high energy propellant to reduce erosion of gun barrel. The composite microcapsules were obtained by an eco-friendly method. Embedding heat-resistant TiO2 and Si3N4 nanoparticles in polystyrene shell enhances the reliability of polymeric shell. The anti-erosion effect of composite microcapsules for high energy propellant was investigated by using an erosion tester. Results showed that the erosion property of high energy propellant with composite microcapsule was significantly decreased when compared to control sample (without microcapsules). It showed a decrease of 20.6% in erosion mass when 7wt.% of composite microcapsules were added to the high energy propellant. Moreover, the anti-erosion efficiency of composite additives exhibited an increasing trend with the increase of their contents. The pressure and time history confirmed that the composite microcapsules also have ability to adjust the combustion performance of high energy propellants. The developed silicon oil microcapsule shows a potential application for propellant erosion additive.