Emerging tribovoltaic nanogenerator (TVNG) technology, which can capture mechanical energy at dynamic semiconductor interfaces and generate instant direct current (DC) outputs, is considered promising to mitigate growing energy demand. However, the unsatisfactory charge excitation and extraction efficiency limit its electrical output stability and even practicability. Here, a novel strategy is proposed to synergistically modulate charge generation and transfer dynamics by integrating ferroelectric and photovoltaic effect with tribovoltaic effect, and thus a multi‐effect coupled Schottky TVNGs is, for the first time, developed. Research indicates that such coupling mechanism involving ferroelectric polarization, photoexcitation, and triboelectricity can allow TVNGs to jointly collect light and mechanical energy to excite more charges, and meanwhile, incorporation of strong electric fields can also be induced by controlled polarization to assist Schottky junction in modulating separation/extraction efficiencies of these charges. Ultimately, this multi‐effect coupled devices deliver impressive DC output of 7.3 V and 69.8 µA, outperforming similar coupled Schottky junction TVNGs. Besides that, its feasibility for multifunctional sensing and photodetection is also demonstrated. This study proposes an effective strategy for modulating performance while extending its functionality, which can expedite the development and potential application of advanced TVNGs.