As a highly reactive metal fuel, aluminum-lithium (Al-Li) alloy is an ideal candidate for replacing Al powders in solid propellants. However, the Li solid solution and AlLi compounds on the surface of Al-Li alloy powders display high reactivity, which can react with a large number of organic and inorganic reagents. Thus, the incompatibility of Al-Li alloy with other components of propellants makes it difficult to be further applied in propellants. In this study, surface-modified Al-Li alloy powders (Li content of 5 wt%) with 1H,1H,2H,2H-perfluorodecyltrimethoxysilane (FAS17) were prepared by a facile self-assembly method, which made the alloy powders super-hydrophobic. The results of SEM, XPS and FIB-TEM show that the surface of Al-Li alloy powder is well-coated by an evenly distributed FAS17 layer. Due to the fluoroalkyl on the surface of the powders, the water contact angle increased by 91 degrees and the intensity of the reaction between alloy powders and water is significantly reduced, which results in improved compatibility with other components of propellants. Meanwhile, the propellant grain of surface-modified powders had fewer defects than the sample before coating, and showed original excellent combustion performance. The average combustion pressure and pressurization rate increased by 114 kPa and 8613 kPa/s, and the steady burning rate increased by 0.24 mm/s. Therefore, the surface-modified Al-Li alloy powders with FAS17 are expected to be an attractive candidate as a highly active and stable fuel in solid propellants.