A new class of AgCl-based composite photocatalysts has been quickly and easily obtained by using nanosized silver(I) exchanged a-zirconium phosphate as a precipitating agent. Different ZP/xAgCl composite catalysts, having AgCl/ZP molar ratio (x) ¼ 0.28, 0.56, and 1.16, were prepared and characterized by X-ray diffraction analysis, scanning electron microscopy/energy dispersive X-ray spectroscopy, and UV-Vis diffuse reflectance spectroscopy. The photocatalytic properties of the ZP/xAgCl composites, having particle size #1 mm, were investigated in the degradation of Rhodamine B, and compared with those of an AgCl sample, with particle size ranging from 0.5 to 2 mm. The ZP/1.16AgCl turned out to be the best photocatalyst, providing a complete chromophore structure cleavage in 15 minutes; differently, in the presence of the pure AgCl sample, the concentration of the chromophore species after 30 minutes was about half of the initial one. Moreover, the catalytic activity of ZP/1.16AgCl was evaluated for three consecutive catalytic tests, and an almost complete chromophore structure cleavage was achieved in 10 minutes during the third run.