Novel V₂O₅ bifunctional photocatalysts were prepared following a wet chemical process with the addition of anionic or non-ionic surfactants into the precursor solution and further heating under reflux. Detailed characterization and investigation of the relevant light-matter interactions proved that surfactants addition had a strong impact on the morphology, while also affecting the crystallinity, the optoelectronic properties, and the surface chemistry of the novel photocatalysts. The most efficient photocatalyst (T80) was based on tween 80, a surface-active agent employed for the first time in the synthesis of vanadium oxide materials. T80 presented crystalline nature without structural defects, which are usually centers of e⁻ − h⁺ recombination. This material also exhibited small crystal size, high porosity, and short migration paths for the charge carriers, enabling their effective separation during photocatalysis. Under UV light illumination, T80 was capable to reduce hexavalent chromium to trivalent up to 70% and showed high yields in degrading methylene blue azo-dye and tetracycline antibiotic water pollutants. This remarkably high bifunctional performance defines T80 as a promising and capable photocatalytic material for both advanced oxidation and reduction processes (AOPs-ARPs).