Phosphates have been used for catalyst, adsorbent and so on. These applications required a large specific surface area of materials. Therefore, to improve their specific surface area, malonic acid, propionic acid, glycine, n-butylamine and urea were added to the preparation of tetravalent cerium phosphate from ammonium cerium nitrate and phosphoric acid solutions. These additives were selected from the viewpoint of the functional groups; in short, acidic sites at both ends of their chemical structures, one-sided acidic site, acidic and basic sites, one-sided basic site and basic sites. The addition of acidic and basic compounds was studied on the chemical composition, powder and functional properties of tetravalent cerium phosphates. By the addition of malonic acid, trivalent cerium orthophosphate was obtained. The specific surface area of the sample prepared with n-butylamine had ten times as large as that of the sample prepared without additives.