One-pot efficient transformation of glucose into 1,1,2-trimethoxyethane via epimerization, retro-aldol condensation (RAC), acetalization, and etherification processes over W-Beta catalysts in the methanol phase was proposed. Uniform dispersive 0.5 wt% tungsten species stabilized by the silanol nests of the Beta zeolite support led to a high 1,1,2-trimethoxyethane (C₅H₁₂O₃) yield of 54.2% at 200 °C, 4.0 MPa N₂, and 4.0 h. The medium Lewis acid arising from the framework W⁵⁺ facilitated the glucose epimerization and RAC reaction while effectively inhibiting the glucose isomerization into fructose, meanwhile, the weak Brønsted acid derived from the residual silanol nests served as the active site for the etherification. The novel reaction pathway from glucose to 1,1,2-trimethoxyethane through C₄ and C₂ intermediates was also proposed.