Recently, composite-type nanogenerators (NGs) formed from piezoelectric nanostructures and multi-walled carbon nanotubes (CNTs), have become one of the excellent candidates for future energy harvesting because of their ability to apply the excellent electrical and mechanical properties of CNTs. However, the synthesis of NG devices with a high proportion of piezoelectric materials and a low polymer content, such as of polydimethylsiloxane (PDMS), continues to be problematic. In this work, high-piezoelectric-material-content flexible films produced from Pb(Zr,Ti)O3 (PZT)-atomically-interconnected CNTs and polytetrafluoroethylene (PTFE) are presented. Various physical and chemical characterization techniques are employed to examine the morphology and structure of the materials. The direct growth of the piezoelectric material on the CNTs, by stirring the PZT and CNT mixed solution, results in various positive effects, such as a high-quality dispersion in the polymer matrix and addition of flexoelectricity to piezoelectricity, resulting in the enhancement of the output voltage by an external mechanical force. The NGs repeatedly generate an output voltage of 0.15 V. These results present a significant step toward the application of NGs using piezoelectric nanocomposite materials.