Triboelectric materials with high charge density are the building-block for the commercial application of triboelectric nanogenerators (TENGs). Unstable dynamic processes influence the change of the charge density on the surface and inside of triboelectric materials. The charge density of triboelectric materials depends on the surface and the internal charge transfer processes. The focus of this review is on recent advances in high charge density triboelectric materials and advances in the fabrication of TENGs. We summarize the existing strategies for achieving high charge density in triboelectric materials as well as their fundamental properties. We then review current optimization methods for regulating dynamic charge transfer processes to increase the output charge density: first, increasing charge injection and limiting charge dissipation to achieve a high average surface charge density, and second, regulating the internal charge transfer process and storing charge in triboelectric materials to increase the output charge density. Finally, we present the challenges and prospects in developing high-performance triboelectric materials.