Seeking to increase the triboelectric charge density on a friction layer is one of the most basic approaches to improve the output performance of triboelectric nanogenerators (TENGs). Here, we studied the storage mechanism of triboelectric charge in the friction layer and discussed the function of carrier mobility and concentration in the charge-storing process. As guided by these results, a kind of composite structure is constructed in the friction layer to adjust the depth distribution of the triboelectric charges and improve the output performance of TENGs. To further elucidate this theory, a simple TENG, whose negative friction layer is a composite structure by integrating polystyrene (PS) and carbon nanotubes (CNTs) into polyvinylidene fluoride (PVDF), was fabricated, and its performance test was also carried out. Comparing with a pure PVDF friction layer, the composite friction layer can raise the triboelectric charge density by a factor of 11.2. The extended residence time of electrons in the friction layer is attributed to a large sum of electron trap levels from PS.