Ultraviolet (UV) nonlinear-optical (NLO) materials are crucial in laser technology due to their ability to modulate light frequency. In this work, when d10 cations, hydroxyl groups, and Cl atoms were combined, a cadmium double salt, Cd(OH)Cl, was synthesized by a simple hydrothermal method. It has a large phase-matched second-harmonic-generation (SHG) response at 1064 nm (2.5 × KDP) with a short UV-cutoff edge (260 nm), which can be applied in a solar-blind UV band. Theoretical calculations suggest that [Cd(OH)3Cl3] groups lead to a large SHG response. Our work may shed light on the exploration of new NLO materials in metal hydroxyl chlorides.