The integration of organic molecules into monolayers on triboelectric layers and electrodes has significantly improved the performance of triboelectric nanogenerators (TENGs) in recent years. By modifying surfaces at the molecular level, one can enhance durability, power density, and cost‐efficiency, leading to flexible, lightweight, and more efficient devices. A simple chemistry of organic monolayer formation allows a precise control over orientation, coverage, consistency, and functionality. These monolayers boost surface charge density and output voltage while influencing surface polarization and dipole interactions. This review focuses on recent advances in chemical modification of electrodes for controlling surface charge density and altering surface dipoles, emphasizing the significance of organic monolayers. A new concept of Schottky‐based TENGs is also introduced that explores chemically modified sliding surfaces. Furthermore, the importance of flexoelectricity and its contribution to triboelectricity is discussed. By addressing current challenges and outlining future directions, this review underscores the crucial role of surface chemistry in advancing TENGs.