Electrochemical reduction of Cr(VI) is eco-friendly and cost-effective for eliminating the environmental risk of Cr-contaminated water. Herein, a novel Ni3S2/MoS2nanowire electrode with a unique stem-leaf structure was synthesized for this purpose. Self-supported ultra-long Ni3S2nanowires bearing MoS2nanoflakes were in-situ grown from Ni foam with a hydrothermal method, in which Ni3S2and MoS2grow accompanied with each other by sharing some S atoms. Consequently, highly conductive out-stretched MoS2nanoflakes wrap the Ni3S2nanowires, providing aligned pathways for directional electron transfer and huge networks for the efficient reduction of Cr(VI) and high uptake of generated Cr(OH)3. The highest Cr(VI) removal rate attained at − 1.2 V approaches 0.005 mg/cm2min, and elimination efficiency of total Cr is high up to 90.81 %. Although the adsorbed Cr(OH)3on Ni3S2/MoS2decreases the activity after repeated runs, the electrode can be restored by a simple pickling process with dilute acid, which has promising application prospects in the electrochemical reduction of Cr-contained wastewater.