Porous and rod-shaped nanostructure of BaAl2O4 was successfully synthesized by using a simple hydrothermal method. Ag-doped BaAl2O4 catalyst based on the porous BaAl2O4 was prepared by incipient wetness impregnation strategy, which showed excellent photoelectric property and catalytic activity. The structural properties of the samples were systematically investigated by XRD, BET, SEM, EDX, TEM, DRS, XPS and FT-IR techniques. The results revealed that the prepared Ag/BaAl2O4 nanorods were more active than BaAl2O4 and commercial TiO2 in photocatalytic oxidation of gaseous toluene. The photodegradation ratio of toluene over Ag/BaAl2O4 reaches to 88%. The toluene was not complete degradation over these catalysts which only partial oxidations were achieved under UV illumination. The weakly adsorbed benzaldehyde is formed during photocatalysis. Hydroxyl groups on the surface of the catalyst are able to react with benzaldehyde which played a key role in the photocatalytic process. (C) 2014 Elsevier Ltd. All rights reserved.