LiFePO₄ nanoparticles with different morphologies and sizes were synthesized via a solvothermal method using environmentally benign and low-cost glycerol as the surfactant. The morphology, size, and structure of the particles were found to relate closely to the concentration of glycerol. Oriented linked LiFePO₄ nanorods along mostly non-[010] were obtained with the proper concentration of glycerol. The nanorods showed good electronic and ionic conductivities, resulting in superior rate capability and cycling performance. This performance was attributed to the oriented linkages along mostly non–[010], the small particle size along [010], and the occupation of Li at Fe sites. Initial discharge capacities of 162.4 mA·h·g^–1 at 0.1 C and 102.1 mA·h·g^–1 at 30 C were achieved, with capacity retentions after 500 cycles at 5 and 20 C of 99.5% and 93.2%, respectively. At the rate of 40 C, the solid-solution phase transition dominated during lithiation and delithiation of all samples.