C-O σ-bonds in multifaceted benzoin derivatives can be effectively cleaved as acetates using catalytic amounts of [Ru(bpy)3]Cl2 as photoredox catalyst in combination with Hantzsch ester and triethylamine as a sacrificial electron donor. This mild and operationally simple method is applicable to a great variety of substrates. Homo- and cross-benzoins, which are easily accessed by NHC (N-heterocyclic carbene) catalysis, with both electron-withdrawing and electron-donating substituents, including aryl halogenides, can be employed. The deoxygenated counterparts are isolated in good to excellent yields. These broadly accessible, α-substituted (nonsymmetric) aryl ketones are versatilely applicable for further transformations as illustrated by the syntheses of 2-arylbenzofurans.