The advanced coupled conversion technique based on the oxidative dehydrogenation (ODH) of alcohols and the reduction of CO₂ is a potential strategy to solve the current energy and environmental crisis, and is of great significance for the upgrading conversion of CO₂ to fuels. This work discloses that the Al³⁺ species-doped decatungstates (Al-DTs) can efficiently catalyze the coupled conversion of various aliphatic and aromatic primary/secondary alcohols with CO₂ in MeCN under visible light illumination and very mild conditions, and the reductive efficiency of CO₂ depends on the doping levels of Al³⁺ species in Al-DTs and the ODH reactivity of alcohols. After continuously illuminating for 12 h, the best, 4% Al-DT can provide 437 μmol acetophenone as the ODH product and 218 μmol CO₂ reduction products (formic acid and methanol) with 1.82 h⁻¹ turnover frequency in the photocatalytic coupled conversion of α-phenylethanol with CO₂. Also, a trace amount of CO is detected from the photocatalytic coupled reactions. UV-vis spectra and isotope tracing tests using heavy oxygen water (H₂¹⁸O) support that the doubly-reduced blue H₂DT species generated from the photocatalytic ODH of alcohols turns into its oxygen-deficient form ([DT²⁻]_v) via an intra-molecular dehydration or lattice oxygen transfer and the latter, with the help of doped Al³⁺ species, may efficiently reduce CO₂ to fuels via the multi-step proton-coupled electron transfer (PET) pathway.