Heterostructures based on ZnO-TiO2/delaminated montmorillonite coated with Ag have been prepared by sol–gel and photoreduction procedures, varying the Ag and ZnO contents. They have been thoroughly characterized by XRD, WDXRF, UV–Vis, and XPS spectroscopies, and N2 adsorption, SEM, and TEM. In all cases, the montmorillonite was effectively delaminated with the formation of TiO2 anatase particles anchored on the clay layer’s surface, yielding porous materials with high surface areas. The structural and textural properties of the heterostructures synthesized were unaffected by the ZnO incorporated. The photoreduction led to solids with Ag nanoparticles decorating the surface. These materials were tested as photocatalysts for the degradation of several emerging contaminants with different nitrogen-bearing chemical structures under solar light. The catalysts yielded high rates of disappearance of the starting pollutants and showed quite stable performance upon successive applications.