Ga-doped LiFePO4 cathode materials were synthesized using a hydrothermal method. The microstructuralcharacteristics and electrochemical performances were systematically investigated using field emission scanningelectron microscopy, high-resolution X-ray diffraction, energy dispersive X-ray spectroscopy, charge-dischargecycling, cyclic voltammetry, and electrochemical impedance spectroscopy. Among the as-prepared samples,LiFe0.96Ga0.04PO4 demonstrates the best electrochemical properties in terms of discharge capacity, electrochemicalreversibility, and cycling performance with an initial discharge capacity of 125 mAh g-1 and high lithium ion diffusioncoefficient of 1.38 × 10-14 cm2 s-1 (whereas for LiFePO4, these were 113 mAh g-1 and 8.09 × 10-15 cm2 s-1, respectively). Theimproved electrochemical performance can be attributed to the facilitation of Li+ ion effective diffusion induced byGa3+ substitution.