Hydrogen energy is an alternative to carbon-based fuels due to its zero pollution and high energy density. The electrolysis of water, driven by triboelectric nanogenerators (TENGs), is considered as a promising green method for hydrogen production. 2D transition metal carbides/nitrides can be used as catalyst carriers, through interface engineering to prepare molybdenum disulfide/titanium dioxide (MoS2/Ti3C2) composites for accelerating the kinetics of hydrogen evolution reaction (HER). In this work, a multilayered rotating TENG (MR-TENG) is designed to convert rotating mechanical energy into electrical energy for constructing a self-powered hydrogen production system. MoS2/Ti3C2 composites are utilized as electrodes for electrolyzing water, which can enhance the catalytic activity in the HER. The output performance of the MR-TENG and its managed charging performance when integrating with a constant voltage power management module are investigated. Besides the application demonstrations of powering a digital thermometer, an anemometer, and a commercial incandescent lamp, the power-managed MR-TENG is applied to generate electricity for water electrolysis, and realize a hydrogen evolution rate of 7.1 mL min−1 at the rotation speed of 90 rpm. This work provides an effective approach to the self-powered production of high-purity green hydrogen based on renewable blue energy utilization with important industrial application prospects.