The ordered three-dimensional photonic crystals with infrared photonic band gap was prepared from 3.87 μm polystyrene (PS) microspheres by vertical substrate self-assembly method. It is found that the microspheres exhibit the highest order and least defect when the ratio of ethanol to water in the suspension is 2:8 (V%). With increasing the concentration of microspheres in the suspension, the number of stacking layers and the thickness of the photonic crystals were improved. Then the reflection and radiation properties of the photonic crystals with different ordering degree in the infrared band were characterized. The results reveal that higher ordering degree and larger ordered area of the microspheres lead to higher reflectivity and lower emissivity of the photonic crystals, thereby effectively inhibiting the infrared radiation of the aim surface.