Two-dimensional (2D) niobium disulfide (NbS2) materials feature unique physical and chemical properties leading to highly promising energy conversion applications. Herein, we developed a robust synthesis technique consisting of electrochemical exfoliation under alternating currents and subsequent liquid-phase exfoliation to prepare highly uniform few-layer NbS2 nanosheets. The obtained few-layer NbS2 material has a 2D nanosheet structure with an ultrathin thickness of ∼3 nm and a lateral size of ∼2 μm. Benefiting from their unique 2D structure and highly exposed active sites, the few-layer NbS2 nanosheets drop-casted on carbon paper exhibited excellent catalytic activity for the hydrogen evolution reaction (HER) in acid with an overpotential of 90 mV at a current density of 10 mA cm–2 and a low Tafel slope of 83 mV dec–1, which are superior to those reported for other NbS2-based HER electrocatalysts. Furthermore, few-layer NbS2 nanosheets are effective as bifunctional electrocatalysts for hydrogen production by overall water splitting, where the urea and hydrazine oxidation reactions replace the oxygen evolution reaction.