Cr(VI) has several industrial applications but it is one of the most dangerous pollutants because of its carcinogenicity and high toxicity. Thus, the removal of Cr(VI) by photocatalytic reduction was investigated. The catalyst applied, Ce–ZrO2, was immobilized, through a sol–gel process on a silicon carbide (SiC) support, to increase the efficiency and avoid using suspended nanoparticles. The influence of initial pH, humic acid (HA), and catalyst dosage was investigated for Cr(VI) containing solutions. Then, a real galvanizing industry effluent (Cr(VI) = 77 mg L-1mg.L−1, Zn = 1789 mg L−1) was treated. It was observed that Cr(VI) adsorption and photoreduction are greatly favored at low pH values. HA can decrease Cr(VI) adsorption but also acts as holes scavenger, reducing the electron–hole recombination, favoring then the photoreduction. With the immobilized Ce–ZrO2, more than 97% of Cr(VI) was removed from the diluted effluent. These results indicate the feasibility to treat Cr(VI) effluents even in the presence of other metals and natural organic matter. The developed material has great chemical and mechanical resistances and avoids the use of nanoparticles, dangerous for the environment and hard to recover. Moreover, solar light can be used to drive the process, which contributes to the development of more sustainable, cleaner, and cost-effective wastewater treatments.