The olivine LiFePO₄ now stands as a competitive candidate of cathode material for the next generation of a green and sustainable lithium-ion battery system due to its long life span, abundant resources, low toxicity, and high thermal stability. In this review, we focus on LiFePO₄ and discuss its structure, synthesis, electrochemical behavior, mechanism, and the problems encountered in its application. The major goal is to highlight some recent development of LiFePO₄ with high rate capability, high energy density, and excellent cyclability resulting from conductive coating, nanocrystallization, or preparation.