The tribovoltaic nanogenerator (TVNG) is emerging as a promising circuit-integrative energy harvester, with notable advantages like direct current output and large current density. Nevertheless, the research on optimizing charge excitation and carrier transportation remains deficient. In this work, we report an alternative approach for practically promoting the output performance of silicon (Si)-based TVNG. A well-designed asymmetric heterostructure is achieved by inserting an appropriate interlayer between the friction layer and the bottom electrode. Carrier extraction efficiency has been promoted effectively, while carrier recombination has been restrained owing to the built-in electric field excited by p-Si/ZnO heterojunction. The coupling mechanism of the built-in electric field and the interfacial electric field has been revealed explicitly with a comprehensive theoretical model, which is based on the capacitance feature of the PN junction. The designed multilayer TVNG (MTVNG) has shown 20 times higher output compared to normal Si-based TVNGs. Apart from presenting fundamental insights into the tribovoltaic effect, we have developed a dual-mode analysis method for vibration monitoring. This work expands the path to improve TVNG output through multi-electric field coupling and provides new inspiration for miniaturized vibration sensors in real-time deployments.