Nb2O5 based solid superacids (Nb2O5-MOx, M = Ti, W, Zr, Si, Al and Ca, respectively) were synthesized by sol-gel method using citric acid as the cross-linking agent, and then were investigated for catalytic combustion of 1,2-dichloroethane (abbreviation: DCE), one of the typical examples for chlorinated VOCs pollutants. The research results of the structure-performance relationship show that mesopore and amorphous state structure are formed for Nb2O5-MOx, and the metal elements are highly dispersed, which contribute to enhancing the metal-metal interaction and modifying the physicochemical properties of the catalysts. The order for the inherent catalytic activity is: Nb2O5-WO3 > Nb2O5-ZrO2 > Nb2O5-TiO2 > Nb2O5-SiO2 > Nb2O5-Al2O3 > Nb2O5 > Nb2O5-CaO. There exists synergistic catalytic effect: the mesopore and surface acidity facilitate the adsorption, activation and destruction of the C-Cl bond in the reactants to form HCl and byproduct C2H3Cl (or carbocation intermediate), and then the redox sites promote deep oxidation of the byproduct/intermediate to convert to CO2 and H2O. Especially, the Nb2O5-TiO2 catalyst represents the highest apparent catalytic degradation activity. It also represents good thermal stability and durability for DCE destruction as well as good resistance to water vapor.