A series of W and Sn-containing KIT-6 mesoporous silicates (designated as WxSn5) with similar Sn (similar to 5 wt %) and varying W (x = 3-23 wt%) loadings were prepared by a one-pot hydrothermal synthesis method. No detectable bulk WO3 species were observed for W loading up to 14 wt% with preferential dispersion of WOx species near SnO2 sites. The WxSn(5) materials exhibited superior performance for Friedel-Crafts anisole benzylation with intrinsic rate constants for all WxSn(5) catalysts being greater than those without Sn. Based on results from DR-UV-Vis, XRD, XPS, EXAFS techniques, we postulate that the WxSn(5) materials contain both isolated [WO4](2-)/SnO2 and isolated [WO4](2-)/SiO2 as active species, with the former being more active. The relative populations of these two highly dispersed species dictate the overall catalyst activity. The intrinsic activities of the WxSn(5) catalysts are found to scale linearly with total acidity but are mainly dictated by the Lewis acid sites. (C) 2020 Elsevier Inc. All rights reserved.