Ag-modified MnO2 loaded on plate-like ZSM-5 (PZ5) with different Ag/Mn ratios were synthesized by an in-situ growth method and used as catalysts for toluene combustion, as a probe molecule of volatile organic compounds (VOCs). The results showed that Ag doping greatly enhanced the toluene combustion activity (Mn50Agy/PZ5). Among them, Mn50Ag0.04/PZ5 showed the highest catalytic activity for toluene combustion with 90 % conversion of toluene at 234 °C (T90), and the reaction rate calculated per unit mass of Mn was 1.22×10−7 at 220 °C, which was 2.7 times higher than that of MnO2. In addition, Mn50Ag0.04/PZ5 exhibited excellent long-term stability and water resistance. Various characterizations indicated that the excellent performance of Mn50Ag0.04/PZ5 was attributed to its higher Mn2++Mn3+/Mn4+ ratios, higher reducibility, and more active surface adsorbed oxygen species. Finally, in-situ DRIFTS studies confirmed that Ag doping did not alter the catalytic combustion pathway of toluene over the Mn50Ag0.04/PZ5 catalyst but could accelerate the rate of conversion of toluene to the final products because the transfer of electrons from Ag+ to lattice oxygen persuaded the weaken of the Mn-O bond, and then made it easier for bulk lattice oxygen to migrate towards the Ag-MnO2 interface or catalysts’ surface, thus showing the better catalytic performance for toluene combustion.