In order to tailor the surface properties of propellants to meet the requirements of progressive burning and anti-erosion performance of propellant for high loading density tank guns, the surface migration and enrichment effects of fluorinated TiO2 nanocomposite additives with low surface energy toward the air/solid interface of propellants were investigated. Fluorinated TiO2 nanocomposites were prepared by emulsion polymerization and characterized by FT-IR spectroscopy, TEM, and TGA to obtain the information of chemical groups, morphology, and thermal stability. The propellant samples containing the fluorinated TiO2 nanocomposite additives were manufactured by an extrusion process. The migration effect of the fluorinated TiO2 nanocomposite additives was observed by SEM and X-ray energy dispersive analysis. The influence factors on the migration and enrichment properties of fluorinated TiO2 nanocomposite additives in propellants were discussed. The results showed that there exists a gradient distribution of fluorine element in the additive modified propellants, indicating a significant surface enrichment of fluorinated groups inside the propellants. The composition of propellants and the chain structure of fluoropolymer also have a significant influence on the migration and enrichment properties of fluorinated TiO2 nanocomposite additives in propellants. This study can bring forward the research of smart construction of slowing burning and anti-wear layers in the propellants.