One of the main drawbacks of the application of photocatalysis for wastewater treatment is the use of dispersed photocatalysts, which are difficult to remove from effluent after the treatment process and may pose additional toxicity to the receiving bodies. As an alternative, immobilized catalysts can be applied; however, this strategy can increase the difficulties in mass and photo transfer. This work presents the development of an inert and highly porous support for TiO2 immobilization. The produced materials have a high surface area and contribute to diminishing the difficulties in mass and phototransfer during photocatalysis. Different types of polymeric materials were tested as support, and a Taguchi experimental design with an L9 arrangement was used to optimize the immobilization process and evaluate the effect of TiO2 content and the use of bidding agents, ultrasound, and thermic treatment. The grey automotive polyurethane foam proved to be the best support, using 5.0% of TiO2 (wt.%) in the immobilization suspension with Triton X as the binding agent and heat treatment during immobilization. At the optimal conditions, it was possible to achieve total As(III) oxidation (below the analytical detection limit) in 240 min, with nearly 100% As(V) present in solution at the end of the reaction (almost no As adsorption on the catalyst surface). In addition, the catalytic bed was able to promote the As(III) complete oxidation in up to five consecutive cycles without significant leaching or deactivation of the immobilized TiO2.