Nickel–titanium (NiTi) instruments have become the backbone of endodontics due to their exceptional properties, superelasticity, and shape memory. However, challenges such as unexpected breakage, poor cutting efficiency, and corrosion have prompted researchers to explore innovative surface modifications to enhance their performance. This comprehensive review discusses the latest advancements in NiTi metallurgy and their impact on rotary NiTi file systems. Various surface treatment techniques, including ion implantation, cryogenic treatment (CT), thermal nitridation, electropolishing, and physical or chemical vapor deposition, have been investigated to minimize defects, boost surface hardness, and improve cyclic fatigue resistance. Ion implantation has shown promise by increasing wear resistance and cutting efficiency through nitrogen ion incorporation. Thermal nitridation has successfully formed titanium nitride (TiN) coatings, resulting in improved corrosion resistance and cutting efficiency. CT has demonstrated increased cutting efficiency and overall strength by creating a martensite transformation and finer carbide particles. Electropolishing has yielded mixed results, providing smoother surfaces but varying impacts on fatigue resistance. Physical or chemical vapor deposition has proven effective in forming TiN coatings, enhancing hardness and wear resistance. Furthermore, the concept of surface functionalization with silver ions for antibacterial properties has been explored. These advancements present an exciting future for endodontic procedures, offering the potential for enhanced NiTi instruments with improved performance, durability, and patient outcomes.