Porous Ag-ZnO/Ag heterostructures have been synthesized by the combustion approach. The independent silver crystal formation was confirmed by the appearance of an independent peak on the XRD pattern and HRTEM image d-spacing analysis. The low-angle shift on the XRD pattern also confirms the inclusion of silver in the ZnO lattice. Thus, the XRD and HRTEM analyses confirm the formation of the Ag-ZnO/Ag (za) heterostructure. Silver inclusion in the ZnO lattice was also confirmed by the DRS-UV–vis indirect bandgap change from 3.03 to 2.86 eV. The porous nature of the materials is confirmed by the FESEM image. The PL spectra intensity reduction for za indicates the presence of charger transfer. Silver dopant surface distribution and composition were confirmed from the EDS-elemental mapping analysis. The porous ZnO heterostructure also showed better lead detection capacity compared to ZnO. Thus, porous materials have future outlooks for pollutant detection and removal applications.