Monodisperse polystyrene (PS) particle multilayer with coherent structure wasconstructed by Langmuir-Blodgett (LB) method. The reflectance spectra of the particle multilayer with various incident angles indicated that the constructed particle multilayer showed a typical optical character of the conventional multilayer having different refractive index. It was suggested that the particle multilayer was treated as a multilayer constructed by polymer layer and air layer. The fact was strongly supported by a simulation of the corresponding model, which was designed for analyzing optical characterization of the particle multilayer. The refractive index of the particle multilayer with nickel ion was also discussed by simulation, suggesting that a theoretical designing of the particle multilayer with various refractive index would be possible. It was also suggested that coordination of metal ion on the surface of the particle would be enhanced its contribution for increasing the refractive index.