Although the bimetal sulfide is intensively pursued in catalytic systems, synthesis of ultrafine sized bimetal sulfide Janus subunits is still a great challenge. In this work, ultrafine NiS₂/MoS₂ Janus subunits organized on yolk–shell nanospheres (NSs) are synthesized by a novel and facile approach. The greatly reduced particle size of both two-dimensional MoS₂ and one-dimensional NiS₂ on the ultrafine NiS₂/MoS₂ Janus subunits endows the yolk–shell NSs with numerous intimate interfaces of bimetal sulfide hybrids greatly promoting the intimate electronic interaction and dissociation of water molecules. Benefiting from the ultrafine NiS₂/MoS₂ Janus subunits, abundant edge sites and the high density of interfaces, the as-prepared NiS₂/MoS₂ yolk–shell NSs exhibit high electrocatalytic activity with a low η₁₀ value of 135 and 293 mV for the HER and OER, respectively. In addition, a low cell voltage (1.58 V) is achieved by using NiS₂/MoS₂ yolk–shell NSs as both anode and cathode. This study has significant indications in exploring the ultrafine nanoparticles for the water splitting reaction, fuel cells and organic synthesis.