An effective method for the synthesis of LiFe_0.975Rh_0.025PO₄ nanorods to serve as a cathode material for lithium-ion batteries is described. During their preparation, L-lysine was used as the growth director of nanorods. The contribution from chloride ions to the formation of the unique nanorods was also investigated. The samples were characterized using X-ray diffraction, X-ray photoelectron spectroscopy, Mössbauer measurements, scanning electron microscopy, electronic conductivity measurements, and transmission electron microscopy. The pH of the solution played a key role in controlling the particle size of the samples. The sample prepared at a pH of 9.5 exhibited excellent electrochemical performance. It delivered an initial discharge capacity of 143.1 mAh g⁻¹, and a capacity fade of only 7.7% was observed after 200 cycles at 2.5 C over a voltage range of 2.0–4.2 V. Furthermore, its discharge capacity remained stable for values as high as 20 C. The excellent electrochemical performance of LiFe_0.975Rh_0.025PO₄ nanorods can be attributed their unique nanorod structure, which limits the distance of lithium ion diffusion in the electrode material to the radius of the nanorods and decreases the surface-film resistance for the charge-transfer process.