Obtaining a comprehensive understanding of the energy storage mechanisms, interface compatibility, electrode-electrolyte coupling, and synergistic effects in carefully programmed nanoarchitectural electrodes and complicated electrolyte systems will provide a shortcut for designing better supercapacitors. Here, we report the intrinsic relationships between the electrochemical performances and microstructures or composition of complex nanoarchitectures and formulated electrolytes. We observed that isolated TiNb2O7 nanoparticles provided both a Faradaic intercalation contribution and a surface pseudocapacitance. The holey graphenes partitioned by nanoparticles not only fostered the fast transport of both electrons and ions but also provided additional electrical double-layer capacitance. The charge contributions from the diffusion-controlled intercalation process and capacitive behaviors, double-layer charging, and pseudocapacitance, were quantitatively distinguished in different electrolytes including a formulated ionic-liquid mixture, various nanocomposite ionogel electrolytes, and an organic LiPF6 electrolyte. A steered molecular dynamics simulation method was used to unveil the underlying principles governing the high-rate capability of holey nanoarchitectures. High energy density and high rate capability in solid-state supercapacitors were achieved using the Faradaic contributions from the lithium-ion insertion process and its surface charge-transfer process in combination with the non-Faradaic contribution from the double-layer effects. The work suggests that practical high-voltage supercapacitors with programmed performances and high safety can be realized via the efficient coupling between emerging nanoarchitectural electrodes and formulated high-voltage electrolytes.