Introducing new inexpensive materials for supercapacitors application with high energy density and stability, is the current research challenge. In this work, Silver doped carbon xerogels have been synthesized via a simple sol-gel method. The silver doped carbon xerogels are further surface functionalized with different loadings of nickel cobaltite (1 wt.%, 5 wt.%, and 10 wt.%) using a facile impregnation process. The morphology and textural properties of the obtained composites are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and nitrogen physisorption analysis. The silver doped carbon xerogels display a higher surface area and larger mesopore volume compared to the un-doped carbon xerogels and hierarchically porous structure is obtained for all materials. The hybrid composites have been utilized as electrode materials for symmetric supercapacitors in 6 M KOH electrolyte. Among all the hybrid composites, silver doped carbon xerogel functionalized with 1 wt.% nickel cobaltite (NiCo1/Ag-CX) shows the best supercapacitor performance: high specific capacitance (368 F g−1 at 0.1 A g−1), low equivalent series resistance (1.9 Ω), high rate capability (99% capacitance retention after 2000 cycles at 1 A g−1), and high energy and power densities (50 Wh/Kg, 200 W/Kg at 0.1 A g−1). It is found that the specific capacitance does not only depend on surface area, but also on others factors such as particle size, uniform particle distribution, micro-mesoporous structure, which contribute to abundant active sites and fast charge, and ion transfer rates between the electrolyte and the active sites.