The preparation of SiO2⋅potassium cobalt hexacyanoferrate (SiO2·KCoFC) composites with a high loading of KCoFC on porous silica is described. This method involves the soaking of silica to a wet state with a concentrated solution of K4Fe(CN)6, drying and then reacting the dried material with a Co(NO3)2 solution prepared in acetone. The composites, B4 and B6 were prepared by single and multi-step deposition of K4Fe(CN)6, respectively, followed by precipitation with the Co(NO3)2 solution. The composites (B8/p1 to B8/p4) were prepared by alternate deposition and precipitation steps. After four such steps, the composite B8/p4 was obtained with the highest KCoFC loading of 1.36 g-KCoFC/g-SiO2. All the composites prepared had a non-stoichiometric composition of KCoFC. The type of coating mechanism was established to be dominantly inhomogeneous or plug coating. The cesium uptake capacity of the silica base and some selected SiO2·KCoFC composites was determined. The capacity of the composite B8/p4 was found to be 0.38 meq Cs/g-composite. The removal efficiency of Cs by the composite B8/p4 was judged by measuring its distribution coefficient, Kd (ml/g-composite) from varying concentrations of HCl, HNO3, NaCl and KCl solutions. The Kd of Cs for HCl in the concentration range of 0.001 to 3 M lies between 7.5×104 and 5.8×104. However, in the case of HNO3, the Kd of Cs decreases when the concentration exceeds 0.1 M. For NaCl in the concentration range of 0.001–1 M, the Kd of Cs remains almost constant (3×104). However, it decreases in the 1–2 M range, and again attains a constant value of about 1.99×103 in the 2–3 M NaCl concentration interval. While the Kd of Cs for 0.001–0.01 M KCl lies between 2–3×105, it decreases when the concentration exceeds 0.03 M and reaches a value of 2×103 in 3 M KCl solution.