<p>Herein, a series of highly porous and well-structured mesoporous materials are presented as supports for chromium catalysts for the mild oxidative dehydrogenation of propane using CO₂ as the oxidizing agent. The materials MCM-41, SBA-1, and SBA-15 were proposed as supports for the preparation of Cr-based catalysts with a Cr content of 6 wt%. These results highlight that mesostructured supports influence chromium species’ dispersion and electronic state in the catalysts. Among the catalysts tested, the Cr/SBA-1 catalyst demonstrated superior propane conversion and propylene selectivity. The results suggest that the Cr⁶⁺ species fraction significantly influences the conversion and selectivity during oxidative dehydrogenation of propane by CO₂. As the Cr⁶⁺ species fraction increases, a linear increase in conversion was observed for both propane and CO₂. Furthermore, an increase in the Cr⁶⁺ species fraction leads to an increased selectivity towards propylene formation while it reduces the selectivity for CO and cracking products. This indicates that Cr⁶⁺ species favor olefin formation over undesired by-products.</p>