The development of highly active and long-lived multifunctional electrocatalysts is a key priority to boost clean renewable energy technologies. It is difficult to construct such hierarchically structured materials with an efficient synergistic heterostructure technique to improve electrochemical performance. Here, a novel hierarchical NiCo-LDH@MoS2/CuS heterostructure (HS) was prepared by facile two-step hydrothermal synthesis for water splitting and supercapacitor applications. The hierarchical network of NiCo-LDH is grown on MoS2/CuS and is put forward based on various physio-chemical analysis. The hierarchical structure and heterostructure synergistic effect result in excellent HER (114 mV@10 mA cm−2) and OER (310 mV@10 mA cm−2) activity. Two electrode water-splitting cells (NiCo-LDH@MoS2/CuS||NiCo-LDH@MoS2/CuS) achieved a cell potential of 1.57 V@10 mA cm−2. NiCo-LDH@MoS2/CuS also exhibits the electrochemical charge storage property of 147.16 mAh g−1@0.2 A g−1. NiCo@MoS2/CuS||AC flexible solid-state asymmetric supercapacitor (FSSC) demonstrated charge storage of 226.08 mAh g−1 and energy density of 152.60 W h kg−1@0.2 A g−1 with 90.05 % retention rate, demonstrated the excellent cyclic and structural stability. The acquired knowledge from this study could be a novel strategy for designing hierarchical LDH-based heterostructures as electrode materials for water splitting and energy storage devices.