Layered double hydroxides (LDHs) have been extensively investigated for various applications such as drug delivery, energy storage, catalysis, and luminescence. In this study, an eco-friendly ZnAl–CO₃–LDH–poly(vinylidene fluoride) (ZnAl–LDH–PVDF) composite acting as a triboelectric dielectric material is described. The composite material can realize a high-performance, flexible, and transparent triboelectric nanogenerator (TENG). The strong interactions between ZnAl–LDH and PVDF facilitate the formation of a spontaneous polar β-PVDF phase and enhance the dielectric properties of composite films considerably. The output performance of ZnAl–LDH–PVDF composite-based TENGs with various amounts of ZnAl–LDH was investigated. 20 wt% ZnAl–LDH–PVDF TENG demonstrated an output voltage of ∼230.6 V, current density of ∼5.6 μA cm⁻², and power density of 0.43 mW cm⁻². The pressure- and humidity-dependent outputs of the device enable it to be an effective self-powered pressure and humidity sensor. As a pressure sensor, the device revealed an excellent pressure sensitivity of 13.07 V kPa⁻¹. As a humidity sensor, it exhibited a response of 259.4% in the voltage detection mode. The improved polar β-PVDF phase and dielectric properties of the ZnAl–LDH–PVDF composite make it suitable for high-performance mechanical energy harvesters in self-powered sensor applications.