In this study, a hierarchical cactus-like nanostructure with cobalt doped iron disulfide (Co-FeS2) needle nanowires as trunks and nickel-iron layered double hydroxide (NiFe-LDH) nanosheets as branches was constructed as a self-supporting electrode for overall water splitting in alkaline electrolytes. A low electron density NiFe-LDH derived from the strong electronic interaction between sulfides and NiFe-LDH is remarkably effective in facilitating the adsorption of H2O and OH−, while the presence of Co atoms in FeS2 facilitates the hydrogen adsorption. Such a synergetic effect improved the HER performance in alkaline electrolytes significantly. In terms of the OER process, the Fe/Co oxyhydroxides produced from in situ phase transition from Co-FeS2 in conjunction with NiFe-LDH endow the electrode with excellent OER activity. Furthermore, the Co-FeS2 needle nanowires with metal-like conductivity allow for rapid electron transfer during electrochemical processes, and the hierarchical structure exposes substantial active sites and facilitates electrolyte penetration. In alkaline media, the electrode demonstrated outstanding HER and OER catalytic activity, requiring small overpotentials of 131 mV and 220 mV to reach current densities of 10 mA cm−2 and 20 mA cm−2, respectively. Moreover, it only needed 1.58 V to drive 10 mA cm−2 when utilized simultaneously as both cathode and anode for overall water splitting.