The application of surface heat reflective coatings is one of the effective measures to solve the temperature disease of concrete structures in sunlit environments. To achieve strong bonding, high durability, and good cooling characteristics, a novel inorganic reflective thermal insulation coating was prepared using magnesium phosphate cement (MPC) as the binder and reflective matrix, and titanium dioxide and glass beads as the reflective thermal insulation reinforcement functional additives. The optimum ratio of the new reflective thermal insulation coating was preferred through laboratory irradiation test, thermal conductivity test, and spectral reflectance test. The results show that MPC itself was a good reflection cooling material, and the surface and internal temperatures of concrete blocks were reduced by 7.6 °C and 6.6 °C, respectively, after using MPC as the cooling coating. When 2% titanium dioxide was added to MPC, the surface and internal temperatures were further reduced by 6.0 °C and 4.9 °C, respectively. On top of this, the surface and internal temperatures of the concrete were reduced by a further 3.9 °C and 2.2 °C when 8% glass beads were added. The bond strength of the MPCTG coating to the concrete matrix reached 2.1 MPa. Finally, the microscopic characteristics and the reflective thermal insulation mechanism of the MPCTG coating were investigated with the aid of SEM, thermo gravimetric analysis, and XRD analysis. The results show that the MPC in the MPCTG coating was well hydrated, and a large number of hydration products encapsulated the unreacted MgO particles, titanium dioxide, and glass beads, forming a dense whole with high reflection and low thermal conductivity, and the coating effectively prevented the entry of radiant heat. At the same time, the MPCTG coating was thermally stable below 70 °C. The magnesium phosphate cement-based reflective thermal insulation coating developed in this study has potential application prospects in concrete structure cooling coatings.