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This study developed a highly stable and reusable WO3 on mesoporous cellular foam silica catalyst (MCF-Si) for dilute bioethanol (70%v/v) dehydration to ethylene. WO3/MCF-Si exhibited exceptional performance during reaction, maintaining a high yield of ethylene ranging from 79.6% to 76.3% even in the final cycle over five consecutive cycles (20 h each), operating without requiring regeneration. Characterization of the spent catalyst revealed the preservation of key textural properties and a shift in the acidity profile. The strength of acidity transitioned from weak to strong acidity, while the type of acid sites evolved from Lewis to Bronsted acid sites. However, the remaining acidity remained sufficiently high to promote efficient ethylene production. Additionally, WO3/MCF-Si demonstrated outstanding resistance to coke formation, with a coke content measured below 0.9 wt%. In light of these findings, WO3/MCF-Si emerges as a promising candidate catalyst for developing sustainable processes for converting dilute ethanol to ethylene.