In this paper, we present a combination of theoretical and experimental study of the one-dimensional photonic structure leading to low infrared emissivity of resin/flaky metal composite coatings according to the structural characteristics of the coatings. A prediction model of low infrared emissivity for resin/flaky metal composite coatings is established by using the theories of one-dimensional photonic structure. In order to verify the feasibility of the above model, polyurethane (PU)/aluminum (Al) composite coatings were prepared by using PU and flaky Al powders as adhesives and pigments, respectively. Then the simulated infrared emissivity of PU/Al composite coatings was calculated by using the above model and the experimental value was measured by infrared emissometer. The results indicate that the calculated infrared emissivity is slightly lower than our experimental value, and the reasons are discussed in this paper.