By means of a simple ion-exchange process (using different precursors) and a light-induced chemical reduction reaction, highly efficient Ag@AgCl plasmonic photocatalysts with various self-assembled structures-including microrods, irregular balls, and hollow spheres-have been fabricated. All the obtained Ag@AgCl catalysts were characterized by means of X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, and UV-visible diffuse reflectance spectroscopy. The effect of the different morphologies on the properties of the photocatalysts was studied. The average content of elemental Ag in Ag@AgCl was found to be about 3.2 mol %. All the catalysts show strong absorption in the visible-light region. The obtained Ag@AgCl samples exhibit enhanced photocatalytic activity for the degradation of organic contaminants under visible-light irradiation. The stability of the plasmonic photocatalysts was also investigated in detail.