An effective approach to synthesize polycrystalline Ni-Co-Mo sulfide (NiCoMoS) is developed through doping engineering coupled with chemical transformation. The polycrystalline NiCoMoS with enriched active edge sites is designed and fabricated on a Ni foam (NF) via a facile hydrothermal calcination and post-sulfidation approach, where the polycrystalline NiCoMoO4 precursor is elaborately prepared by doping Co ions into the NiMoO4 lattice and subsequently in-situ-converted into NiCoMoS with 3D architectures of ordered nanoneedle arrays. Benefiting from the unique 3D structure and synergistic effects of each component, the optimized needle-like NiCoMoS(2.0) arraying on a NF as a self-standing electrode exhibits superior electrochemical performances with a high specific charge (920.0 C g-1 at 1.0 A g-1), excellent rate capability, and good long-term stability. Furthermore, the assembled NiCoMoS//activated carbon hybrid device presents a satisfactory supercapacitor performance, affording an energy density of 35.2 W h kg-1 at a power density of 800.0 W kg-1 and competitive long-term stability (83.8% retention at 15 A g-1 after 10,000 cycles). Such a novel strategy may pave a new route for exploring other polymetallic sulfides with enriched, exposed active edge sites for energy-related applications.