AbstractDeveloping active, stable, and cost‐effective water splitting catalysts is a critical step towards a sustainable energy future. Heterostructures of transition metal chalcogenides have emerged as important candidates for catalyzing oxygen evolution reaction (OER) or hydrogen evolution reaction (HER), due to the synergistic effects originating from the increased active sites or accelerated electron transfer. Current limitation to this strategy lies in the complication of synthesis often resorting to the direct growth of hybrid structures on a conductive current collector. Here, a simple approach is selected to synthesize graphitic carbon layer coated Ni3S2/MoS2 heterostructures (denoted as NMC) with a facile scaffold‐free solvothermal method followed by controlled pyrolysis. The NMC obtained at 600 °C behave as durable, efficient oxygen and hydrogen evolution electrodes with overpotentials of 350 mV and 233 mV respectively at 10 mA cm−2 in 1.0 M KOH. In addition, the catalysts demonstrate a high efficiency for overall water splitting. Such architected catalyst designs may shed light on the development of more efficient bifunctional electrocatalysts.