There is a growing demand for hybrid supercapacitor systems to overcome the energy density limitation of existing-generation electric double layer capacitors (EDLCs), leading to next generation-II supercapacitors with minimum sacrifice in power density and cycle life. Here, an advanced graphene-based hybrid system, consisting of a graphene-inserted Li₄Ti₅O₁₂ (LTO) composite anode (G-LTO) and a three-dimensional porous graphene-sucrose cathode, has been fabricated for the purpose of combining both the benefits of Li-ion batteries (energy source) and supercapacitors (power source). Graphene-based materials play a vital role in both electrodes in respect of the high performance of the hybrid supercapacitor. For example, compared with the theoretical capacity of 175 mA·h·g⁻¹ for pure LTO, the G-LTO nanocomposite delivered excellent reversible capacities of 207, 190, and 176 mA·h·g⁻¹ at rates of 0.3, 0.5, and 1 C, respectively, in the potential range 1.0–2.5 V vs. Li/Li⁺; these are among the highest values for LTO-based nanocomposites at the same rates and potential range. Based on this, an optimized hybrid supercapacitor was fabricated following the standard industry procedure; this displayed an ultrahigh energy density of 95 Wh·kg⁻¹ at a rate of 0.4 C (2.5 h) over a wide voltage range (0–3 V), and still retained an energy density of 32 Wh·kg⁻¹ at a high rate of up to 100 C, equivalent to a full discharge in 36 s, which is exceptionally fast for hybrid supercapacitors. The excellent performance of this Li-ion hybrid supercapacitor indicates that graphene-based materials may indeed play a significant role in next-generation supercapacitors with excellent electrochemical performance.