We show that a simple ethanol (EtOH) refluxing treatment at mild temperature (120 °C) allows producing blue-colored and reduced titanium dioxide (TiO2-x) exhibiting improved visible-light (VIS) photocatalytic properties. The treatment causes an increase in the density of Ti(III) species and the appearance of two optical absorption features: a broad absorption band--responsible for the blue coloration--extending from the green region (~2.3 eV) up to the near-infrared and a subgap absorption tail close to the band gap energy. The experimental results combined with a computation of the density of states via hybrid Hartree-Fock density functional support the hypothesis that the EtOH reflux treatment leads to formation of surface and subsurface oxygen (O) vacancies. We also show that the excitation-resolved photoluminescence technique allows a high-contrast detection of a subgap optical excitation band peaked at about 430 nm (~2.9 eV), associated with anatase photoluminescence, whose intensity increases after the EtOH reflux treatment. This result gives a very direct support to the debated hypothesis identifying O vacancy states as the energy levels involved in the radiative transition of anatase TiO2. Improved photocatalytic degradation by the processed TiO2 under VIS illumination is demonstrated, and the possible mechanism involved in the formation of surface O vacancies is discussed. The method outlines a very simple, low-cost, and fast procedure to target the formation of O vacancies in the TiO2 surface region.