In this research, Ag‐Al2O3 nanostructures have been prepared via combustion synthesis and ammonium acetate and urea have been applied as fuels. The prepared Ag‐Al2O3 nanostructures were characterized by DTA, XRD, SEM, TEM, and BET spectroscopy. The effect of different ratios of silver to alumina and fuel percentage on morphology and particle size of prepared products were investigated. The results showed that using ammonium acetate fuel led to the production of Ag‐γ‐Al2O3 nanocompounds, while using urea produced Ag‐α‐Al2O3. Also, the photocatalytic activity of Ag‐Al2O3 nanostructures for Congo red degradation was evaluated by UV‐Vis diffuse reflectance spectroscopy. The photocatalytic activity of Ag‐Al2O3 was examined under UV‐Vis irradiation and showed significant photocatalytic efficiency.