The solution combustion synthesis approach successfully synthesized the porous silver-zinc oxide nanocomposites (Ag-ZnO NCs). The pore generation and silver metal reduction occurred due to the evolution of gaseous byproducts during the combustion of poly(vinyl alcohol)-precursor complex. The low-resolution SEM and TEM images confirmed the porous nature of the synthesized NPs ad NCs. The nanoscale crystallite size (30 – 70 nm), crystallinity, and Ag-ZnO NCs heterojunction were confirmed from the XRD pattern and TEM/HRTEM/SAED analysis. The absence of a bandgap change between ZnO and NCs confirmed from the DRS-UV-vis analysis, indicating the non-inclusion of Ag in the ZnO lattice. The photoluminescence spectrum of doped NCs has less intensity than pure ZnO NPs, confirming the presence of charge transfer within the Ag-ZnO NCs, which prevents electron-hole recombination. The Mott–Schottky analysis confirmed the n– and p–type characters of the NCs, unlike that of ZnO NPs, which have only n-type characters. Thus, synthesizing nanomaterials by the solution combustion synthesis approach is a novel method for producing pure and electrical properties improved catalyst, which is beneficial in several applications such as catalysis and sensor.