<p>Nitrate esters, also known as organic nitrates, are an important class of compounds owing to their diverse applications in synthetic chemistry, medicine, and materials science. Traditionally recognized as energetic materials and vasodilators, they have also demonstrated therapeutic potential in pain management, wound healing, and cancer treatment. The synthesis of nitrate esters via C–H functionalization enables direct access to valuable products from simple hydrocarbons. Recent advances in C(<i>sp</i>³)–H functionalization methods have facilitated their formation using various nitrate sources, including HNO₃, <i>t</i>-BuONO, metal nitrites, metal nitrates, and hypervalent iodine reagents. However, existing methodologies are largely restricted to a limited substrate scope, primarily targeting methyl arenes, ethyl carbonyls, 1,3-dicarbonyls, and protected alcohols. This limitation presents a clear opportunity for expanding the range of applicable starting materials. This review summarizes current synthetic strategies for nitrate esters formation through C(<i>sp</i>³)–H functionalization and highlights the potential of these approaches to access previously unattainable nitrate esters.</p>