Fe4[Fe(CN)6]3 coated on a mica or TiO2/mica surface as infrared reflective blue pigment was prepared by a hydrothermal method. Fe4[Fe(CN)6]3, used as coloring agent, was uniformly coated on mica or TiO2/mica under the optimized condition of a 1.2 : 1 weight ratio between iron(III) chloride hexahydrate and potassium ferrocyanidetrihydrate at the initial pH level of 4.5 at 70˚C. The infrared (IR)-reflective pigments were characterized by SEM, Zeta-potenial, FT-IR, and UV-VIS NIR spectrophotometry. Especially the CIE color coordinate and total solar reflectance(TSR) properties of the pigments were investigated in relation to variation of the coating and coated substrate thicknesses. Isolation-heat paint was prepared with 20 wt% blue pigments fully dispersed in acryl-urethane resin and several additives to coat the film uniformly. The films were also measured with CIE color coordinate, TSR, and the surface temperature was recorded by an isolation-heat measuring system. The pigments and films of Fe4[Fe(CN)6]3 coated on mica and TiO2/mica showed high TSR values compared with the TSR value of Fe4[Fe(CN)6]3 itself. According to the increase of TSR value, the property of isolation-heat is effective. To realize the optimal blue color, we applied the the pigment to TiO2 coated mica(TM(b)) which has blueish interference color. The pigment of Fe4[Fe(CN)6]3 coated on TM(b) shows a strong blue color compared with that of Fe4[Fe(CN)6]3 coated on TiO2/Mmca(TM(w)), which has a whitish interference color.