In the wake of the carbon–neutral era, the exploration of innovative materials for energy storage and conversion has garnered increasing attention. While nickel silicates have been a focal point in energy storage research, their application in supercapacitors (SCs) has been relatively underreported due to poor conductivity. A newly designed architecture, designated as rGO@NiSiO@NiO/C (abbreviated for reduced graphene oxide (rGO), nickel silicate (NiSiO), nickel oxide/carbon (NiO/C)), has been developed to enhance the electrochemical performance of NiSiO. The incorporation of inner rGO provides structural support for NiSiO, enhancing conductivity, while the outer NiO/C layer not only boosts conductivity but also safeguards NiSiO from structural degradation and electrolyte dissolution. This architecture eliminates multi-phase mixtures, facilitating rapid electron/mass transfer kinetics and accelerating electrochemical reactions, resulting in exceptional electrochemical properties. The rGO@NiSiO@NiO/C architecture achieves a specific capacitance of 324F·g−1 at 0.5 A·g−1, with a superb cycle performance of ∼ 91 % after 10,000 cycles, surpassing state-of-the-art nickel silicates. Furthermore, the hybrid supercapacitor (HSC) device incorporating the rGO@NiSiO@NiO/C electrode attains an areal capacitance of 159 mF·cm−2 at 2.5 mA·cm−2, a retention ratio of ∼ 98 % after 10,000 cycles, and an energy density of 0.68 Wh·m−2 (26.7 Wh·kg−1) at 3.4 W·m−2 (343.8 W·kg−1). This study presents a layer-by-layer approach for constructing transition metal silicates/C architectures to enhance their electrochemical performance.