Lithium titanium oxide (LTO) batteries offer superior performance compared to graphite-based anodes in terms of rapid charge/discharge capability and chemical stability, making them promising candidates for fast-charging and power-assist vehicle applications. However, commonly used battery models often struggle to accurately describe the current–voltage characteristics of LTO batteries, particularly before the charge/discharge cutoff conditions. In this work, a novel electrical model based on the solid-phase diffusion equation is proposed to capture the unique electrochemical phenomena arising from the diffusion mismatch between the positive and negative electrodes in high-power LTO batteries. The robustness of the proposed model is evaluated under various loading conditions, including constant current and dynamic current tests, and the results are compared against experimental data. The experimental results for LTO batteries exhibit remarkable alignment with the model estimation, demonstrating a maximum voltage error below 3%.