The energy conversion efficiency of conventional binary dielectric triboelectric nanogenerators is not satisfactory due to the limitations of material selection and triboelectrification, which motivates the design of more efficient multicomponent structures to reveal the charge accumulation mechanism for improving the energy conversion efficiency. Herein, a rotating quaternary dielectric triboelectric nanogenerator (Q-TENG) is designed to construct a self-powered system integrating illumination, sensing, and electrochemical decolorization. Through the equivalent capacitance model, the mechanisms for charge generation, transfer, and accumulation in a Q-TENG are elucidated to achieve efficient matching of quaternary dielectric materials and high output performance. At a wind speed of 3.5 m s–1, the peak power density of the Q-TENG reaches 44.94 W m–2, setting a new record for a wind-driven TENG. A 5 ppm solution of methyl orange is completely degraded by the wind-driven Q-TENG in <6 h. This work not only guides the direction for constructing more efficient TENG systems but also promotes the practical development of self-powered electrochemical systems.