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Transition metal doped WO 3 mixed oxides (named as W-M-O, M = Nb, Fe, Cr, Cu, Ti or Sn, respectively) with high structure stability were synthesized by modified sol-gel method using citric acid as organic crosslinking agent, and were evaluated for catalytic elimination of low-concentration toluene, monochlorobenzene and 1,2-dichloroethance with high toxicity and relatively stable molecule structure, as the typical examples for the pollutants of various volatile organic compounds (VOCs). Results of the structure-property-performance relationship research showed that mesoporous structure and nanocrystalline/amorphous state were formed, and binary metal components were dispersed into each other, which contributed to promoting the metal/metal electron interaction and adjusting the physicochemical properties of mixed metal oxides. The sequence of apparent catalytic activity for toluene degradation was: W–Nb–O＞W–Fe–O＞W–Cr–O, W–Cu–O＞W–Ti–O＞W–Sn–O＞WO 3 , and the sequence for monochlorobenzene degradation was: W–Nb–O＞W–Fe–O＞W–Cr–O, W–Ti–O＞W–Cu–O＞W–Sn–O＞WO 3. There existed cooperative catalytic effect: mesopore and surface acid sites of catalysts facilitated adsorption, activation and breakage of the C-X bond, and then redox sites of catalysts promoted deep oxidation of a series of reaction intermediates to transform into CO 2 and H 2 O. Especially, the optimized W–Nb–O catalyst deserved more attention, since it represented remarkable catalytic activity, selectivity and durability for three typical VOCs degradation along with good resistance to water vapor and corrosion of HCl. [Display omitted] • WO 3 based transition metal mixed oxides were prepared by modified sol-gel method. • Interaction between WO 3 and MO x affected the properties of mixed oxides. • WO 3 –Nb 2 O 5 displayed the best catalytic performance for VOCs elimination. • Cooperative catalytic effect was observed in WO 3 –Nb 2 O 5 catalyst system. [ABSTRACT FROM AUTHOR]