In this study, a methodology for fabricating double‐arch triboelectric and piezoelectric composite nanogenerators using polyvinylidene fluoride (PVDF) and graphene oxide (GO) is presented. Initially, nanofiber films comprising PVDF/GO are synthesized through electrostatic spinning. Subsequently, the PVDF/GO film is integrated with cotton fibers and a copper electrode to construct the triboelectric layer. In contrast, another portion of the PVDF/GO film, alongside a copper electrode, comprises the piezoelectric layer, with the central copper electrode acting as a common electrode. Finally, a double‐arch structure is established by employing polyethylene terephthalate film to facilitate synergistic operation between the triboelectric and piezoelectric layers. In the experimental results, it is indicated that the maximum open‐circuit voltage and short‐circuit current of the triboelectric layer of the double‐arch structure are 330 V and 36 μA, respectively, representing increases of 44% and 50% compared to those of the sandwich triboelectric structure. Additionally, the maximum open‐circuit voltage and short‐circuit current of the piezoelectric layer are 22 V and 4 μA, respectively, reflecting enhancements of 57% and 100% over those of conventional sandwich piezoelectric structures. The output power of the double‐arch composite nanogenerator is capable of lighting up 120 light‐emitting diodes. Thus, this composite nanogenerator shows great potential as an environmentally friendly energy source.