Triboelectric nanogenerators have shown great potential in the area of self-powered gas sensors in the past decade. In this paper, we developed a triboelectric nanogenerator (TENG) based on spiky structured ZIF-8@ZnO, which can harvest energy with high efficiency and act as a self-powered methanol sensor. The open-circuit voltage and short-circuit current generated by a ZIF-8@ZnO-based TENG is 58 V and 10 μA, achieving 2.4 times and 3.3 times enhancement compared to ZnO-based TENGs. The TENG can charge capacitors fast and light up at least 40 LEDs. ZIF-8@ZnO-based TENGs show good sensitivity and selectivity to methanol gas at room temperature due to the porous structure provided by ZIF-8 and the heterostructure of ZIF-8@ZnO. The response of ZIF-8@ZnO-based TENG to methanol reaches 30.35% at 100 ppm with excellent response (∼5.9 s) and recovery time (∼2.2 s). This work demonstrates the application of MOF-modified metal oxide semiconductors based on a self-powered gas sensor and proposes a promising solution to enhance the output performance and sensing properties of TENGs based on metal oxide semiconductors.