We developed a book-shaped triboelectric nanogenerator (TENG) that consists of electrospun polyvinylidene fluoride (PVDF) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) nanofibers to effectively harvest mechanical energy. The dispersed graphene oxide in the PVDF nanofibers acts as charge trapping sites, which increased the interface for charge storage as well as the output performance of the TENG. The book-shaped TENG was used as a direct power source to drive small electronics such as LED bulbs. This study proved that it is possible to improve the performance of TENGs using composite materials.