An annular UV photocatalytic reactor with recirculation in batch was designed and built. The design considered low construction, simple operation and maintenance costs, availability and durability of the materials used, easy cleaning, and high standards of hygiene and safety. The TiO2 photocatalysts were synthesized by plasma electrolytic oxidation (PEO) on commercial Ti rings were compared with coatings obtained on Ti plates as a reference, and no influence of the substrate geometry on the morphology, crystallinity, or bandgap of the coatings was observed. The efficiency of the photocatalytic reactor using 10 TiO2-coated rings was tested by Cr(VI) transformation in the presence of EDTA. The Cr(VI) transformation after 5 h irradiation attained 95%; a rather high photocatalytic activity (62%) was maintained after the third use of the rings without reactivation of the photocatalyst. These coatings synthesized by PEO have not been applied in modular photocatalytic reactors until now.