In this study, the importance of the preparation technique of Li₄Ti₅O₁₂ (LTO) anode on its performance in a lithium-ion capacitor (LIC) application was investigated. These desired characteristics include energy density, rate capability, and cycle life. The samples were prepared using three approaches, and the same sol-gel synthesis procedure is applied to obtain phase-pure samples and keep the structural properties similar. The influence of these methods on the LTO anodes was then explored in both half-cell and full-cell LIC devices with an activated carbon (AC) cathode. It was observed that the samples had similar specific capacities and energy densities at low specific currents. However, significant differences were observed in the samples’ morphological properties, the rate capability, and the full-cell cycle life performance. Electrochemical impedance spectroscopy was used to identify the electrochemical kinetics and revealed that the LIC with the best performance was influenced by the LTO anode having the least charge transfer and diffusion resistances prepared using a surfactant. This was due to the small particle size, good particle dispersion, and high specific surface area of the LTO anode. This result points to the importance of the choice of synthesis technique in LIC material’s overall performance.