Embedding additional ferroelectric dipoles in contacting polymer layers is known to enhance the performance of triboelectric nanogenerator (TENG) devices. However, the influence of dipoles formed between the triboelectric surface charges on two contacting ferroelectric films has been ignored in all relevant studies. We demonstrate that proper attention to the alignment of the distinct dipoles present between two contacting surfaces and in composite polymer/BaTiO3 ferroelectric films can lead to up to four times higher energy and power density output compared with cases when dipole arrangement is mismatched. For example, TENG device based on PVAc/BaTiO3 shows energy density increase from 32.4 μJ m−2 to 132.9 μJ m−2 when comparing devices with matched and mismatched dipoles. The presented strategy and understanding of resulting stronger electrostatic induction in the contacting layers enable the development of TENG devices with greatly enhanced properties.