Films with ordered structures were prepared by casting dispersions of binary mixtures composed of poly(4-vinylpyridine) (P4VP) microgel and polystyrene (PSt) microgel with -OH groups on its surface. The diameters and mixing ratios of two components were varied. The ratios of diameters gamma ((diameter of PSt)/(diameter of P4VP)) were 0.73 (VS1 series) and 0.43 (VS2 series). Ordered structures were obtained for both series and the crystal types of these structures were identified by calculating the interparticle angles composed of three particles. The ordered structures in VS1 and VS2 series corresponded to MgCu2 and NaCl crystal types, respectively. The crystal type of the ordered structure was independent of the mixing ratio but dependent on the ratio of the particle diameters, whereas the fraction of ordered phase was affected by the mixing ratio. No ordered structure of long range was found in films of binary systems composed of the microgels with the same composition or similar surface characters.