The existing road surface marking with poor visibility at night results in traffic safety hazards in insufficient lighting roads. This study aims to prepare the dedicated aluminate-based persistent phosphors considering the integrated pavement environment, as the first step to achieve the durable luminescent road surface marking. SrAl2O4: Eu2+, Dy3+ persistent phosphors coated with silica–polymer hybrid shell were prepared by chemical precipitation and sol-gel method to improve moisture resistance and organic compatibility. The optimum silane coupling agent type and dosage, the surfactant dosage, the optimum sodium silicate dosage, and the coating reaction time in silica shell and polymer shell coating were studied based on the moisture resistance test. The silica–polymer hybrid shell coating balances the organic compatibility and thermal stability as compared to the silica or polymer shell coating in the oil absorption test and thermogravimetric analysis. Ex-Em Spectra, XRD, and SEM method were used to characterize the persistent phosphors, indicating the preparation does not destroy the persistent phosphors. The outstanding durable properties of SrAl2O4: Eu2+, Dy3+ persistent phosphors coated with silica–polymer hybrid shell as shown in this research is crucial for its potential application in waterborne luminescent coatings of road surface marking.