As a gaseous second messenger, nitric oxide (NO) plays an important role in a series of signal pathways. Research on the NO regulation for various disease treatments has aroused wide concern. However, the lack of accurate, controllable, and persistent release of NO has significantly limited the application of NO therapy. Profiting from the booming development of advanced nanotechnology, a mass of nanomaterials with the properties of controllable release have been developed to seek new and effective NO nano‐delivery approaches. Nano‐delivery systems that generate NO through catalytic reactions exhibit unique superiority in terms of precise and persistent release of NO. Although certain achievements have been made in the catalytically active NO delivery nanomaterials, some basic but critical issues, such as the concept of design, are of low attention. Herein, an overview of the generation of NO through catalytic reactions and the design principles of related nanomaterials are summarized. Then, the nanomaterials that generate NO through catalytic reactions are classified. Finally, the bottlenecks and perspectives are also discussed in depth for the future development of catalytical NO generation nanomaterials.