On the road to large-scale industrialization of triboelectric nanogenerators (TENGs), higher output is the constant quest. Here, inspired by the ubiquitous synergies in nature, an ultra-high-output TENG is proposed based on the synergistic effect of internal modification of materials along with the external integration of a charge pumping module. The carefully chosen poly (vinylidene fluoride-co-hexafluoropropylene) (P(VDF-HFP)) film possesses strong polarization and high permittivity, which leads to excellent triboelectric properties, and can be further enhanced by doping BaTiO3 (BTO) nanoparticles. Meanwhile, the elaborately designed and optimized charge pumping module endows it with the ability to pump affluent charges. As a consequence, a TENG based on 8 µm P(VDF-HFP)/BTO 1 wt% composite film can achieve an ultra-high total transfer charge density (TTCD) of 3.5 mC/m2 under optimal charge pumping conditions. Compared to the output of the P(VDF-HFP)/BTO-based TENG (0.1 mC/m2) and the output of the P(VDF-HFP)-based TENG under charge pumping (2.6 mC/m2), the output of the P(VDF-HFP)/BTO-based TENG under charge pumping is greater than the sum of the above two devices, which indicates that the proposed synergistic effect for designing an ultra-high-output TENG is remarkable and successful. Moreover, a novel charge transfer pattern based on synergistic effect is proposed, expounding the role inherent modifications of P(VDF-HFP) and external integration of charge pumping modules play. This work presents a concept that is at the forefront of contemporary designs for ultra-high output TENGs, providing insight into the preparation of high-performance TENGs in a state-of-the-art manner.