With the continuous expansion of industrial activities worldwide, industrial emissions of nitrogen oxides (NOx) pose a serious threat to both ecosystems and human health. Ammonia selective catalytic reduction of NO (NH3‐SCR) technology has emerged as the most effective means to reduce NOx emissions, and the development of catalysts is crucial for the successful implementation of this technology. In gas‐solid multiphase catalytic systems, the performance limitations of conventional catalysts can be effectively overcome by meticulously designing the nanostructures of the catalysts to achieve improved catalytic efficiency. In this review, the unique structural features of core‐shell structures, layered double hydroxide (LDHs), hollow nano spheres and nanotubes, along with their preparation processes, are systematically examined, beginning with the effects of structural changes on catalytic performance. Based on this review, the impact of structural modifications on the catalytic efficiency of the catalysts for the NH3‐SCR reaction and their anti‐poisoning performance were investigated. Ultimately, the influence of catalyst structural changes on the future design of catalysts is anticipated. This provides a robust scientific foundation for the conception of higher performance catalysts, paving the way for technological innovation and advancements in NOx emission reduction practices.