Thermal catalytic oxidation at room temperature using a noble metal catalyst is a rapid, stable, and efficient removal strategy for HCHO, a ubiquitous indoor air pollutant. However, the catalytic oxidation optimization through the support defect control has been barely explored. We prepared an oxygen vacancy-rich anatase TiO2 (VO-TiO2) as electron transfer catalyst support for the efficient catalytic conversion of HCHO to CO2 and H2O. VO-TiO2, prepared by chemical vapor condensation with post heat treatment, exhibits void-embedded nanostructures and electron paramagnetic activity, which governs the deposition pattern of Pt nanoparticles upon the impregnation. Pt/VO-TiO2 (0.086 wt% Pt) converted 100% of 10 ppm HCHO at room temperature and 200,000 cm3 h−1 gcat−1 GHSV in >250 min. The X-ray absorption (XAS) studies of used catalysts confirmed the conservation of metallic state of Pt only in oxygen vacancy-rich anatase TiO2 (VO-TiO2). The First-principles density-functional theory calculations revealed that the excess electrons at the oxygen vacancies in VO-TiO2 stabilize the otherwise-vulnerable Pt nanoparticles. This study demonstrates an effective defect control strategy for transforming a TiO2 support into a dynamic electron transfer catalyst platform.