Highly active and low-cost co-catalysts have a positive effect on the enhancement of solar H 2 production. Here, we employ two-dimensional (2D) MBene as a noble-metal-free co-catalyst to boost semiconductor for photocatalytic H 2 production. MoB MBene is a 2D nanoboride, which is directly made from MoAlB by a facile hydrothermal etching and manual scraping off process. The as-synthesized MoB MBene with purity >95 wt % is treated by ultrasonic cell pulverization to obtain ultrathin 2D MoB MBene nanosheets (∼0.61 nm) and integrated with CdS via an electrostatic interaction strategy. The CdS/MoB composites exhibit an ultrahigh photocatalytic H 2 production activity of 16,892 μmol g -1 h -1 under visible light, surpassing that of pure CdS by an exciting factor of ≈1135%. Theoretical calculations and various measurements account for the high performance in terms of Gibbs free energy, work functions, and photoelectrochemical properties. This work discovers the huge potential of these promising 2D MBene family materials as high-efficiency and low-cost co-catalysts for photocatalytic H 2 production.