An efficient method for the prediction of the release characteristics of film-coated urea from its film structure is proposed. A model spray-coating apparatus was built to prepare a plane film to directly measure the film permeability coefficients by simulating the characteristics of randomness, intermittence and multiple layers of the coating, and eliminating particle collision effects. From analysis, the spray-coated film structure can be modeled as comprising a dense structure and a defect structure. Both structures contributed to the penetration flux and the apparent permeability coefficients of the film for water and urea diffusion. The permeability coefficients of the plane films were calculated from the film structure model, and were shown to be close to the measured values.