For improving the night recognition of road markings and enhancing the driving safety of asphalt pavements, single-factor optimization is used to investigate the effects of the component materials, including luminescent power, pigment, filler, and anti-sedimentation agent, on the luminous performance of a coating. Additionally, their composition ratios are optimized using response surface methodology. A phosphorescent marking coating is prepared to investigate the micromorphology, excitation, and emission properties using scanning electron microscopy (SEM) and molecular fluorescence spectroscopy (MFS). The optimum thickness of the coating on an asphalt pavement is investigated, and the durability of the coating on asphalt pavement using a wheel rutting test is evaluated. The results show that the 300 mesh yellow-green luminous powder has the optimal overall performance, with an initial luminescence that exceeds that of orange and sky blue by three times. Initial brightness is mainly influenced by aluminate luminescent powder (ALP), which increases with the dosage. ALP and fumed silica powder (FSP) have a positive effect on brightness after centrifugation, and the effect of FSP dosage is more significant. ALP, rutile titanium dioxide powder (RTDP), and FSP influence the wear value of the coating, and the magnitude of the effect is RTDP > FSP > ALP. The optimal dosages of the main component are 27% ALP, 5% RTDP, and 0.8% FSP. The results of SEM show that the components in the coating are evenly dispersed, and the surface of the coating is rough. The peak excitation wavelength of 420 nm means that the coating has the best excitation effect in UV light, and its emission spectrum in the 440–760 nm wavelength range is well within the sensitive recognition zone of the human eye. The initial brightness gradually reached 4.38 cd/m2 when the coating thickness was increased from 482 μm to 546 μm, and the optimal application thickness of the luminous coating was determined to be 500 μm. At high and normal temperatures, the rutting stripping rates of the luminous marking coating are 16.8% and 8.2%, indicating its satisfactory durability. This study provides an experimental basis for the ratio optimization design of a luminous coating for asphalt pavements.