Electrochemical synthesis is a promising green strategy for organic synthesis, but its sustainability is compromised by its reliance on external power sources. Herein, we designed a double-spiral zigzag-origami triboelectric nanogenerator (DZ-TENG) based on zinc coordination polymer@cellulose acetate (Zn-CP@CA) composite films that can harvest mechanical energy from a vehicle-road pavement interface to drive an electrochemical system. A Zn-CP was synthesized and incorporated into CA at various mass ratios to fabricate a series of Zn-CP@CA composite films. Systematic characterization demonstrated that the 5% Zn-CP@CA composite film exhibited the highest triboelectric performance. Subsequently, a DZ-TENG utilizing the 5% Zn-CP@CA composite film was constructed and its output was optimized by adjusting the contact area and the number of folding layers. The resulting six-layer device DZ-6 delivered the optimal output under human mechanical energy. When mounted on a simulated vehicle setup, the TDZ-TENG device composed of two DZ-6 units harvested mechanical energy and converted it into electricity to drive an electrolytic cell for the site-selective bromination of alkylarenes, affording the corresponding benzyl bromide products in high yields and with excellent regioselectivity. This study presents a feasible method for designing vehicle-road pavement energy harvesters and expands the application of TENGs to sustainable and autonomous electrochemical synthesis.