In this work, LiFePO4 with hierarchical microstructures self-assembled by nanoplates has been successfully synthesized by using poly(vinyl pyrrolidone) (PVP) as the surfactant in a benzyl alcohol system. The resulting dumbbell-like LiFePO4 microstructures are hierarchically constructed with two-dimensional nanoplates with 300 nm length and 50 nm thicknesses, while these tiny plates are attached side by side in an ordered fashion. Both benzyl alcohol and LiI acting as reducing agents promote the formation of LiFePO4, and the presence of PVP plays an important role in the construction of the hierarchically self-assembled microstructures. A reasonable formation mechanism is proposed on the basis of the result of time-dependent experiments. In addition, the cell performance of the synthesized LiFePO4 is better than that of the commercial LiFePO4, which makes it a promising cathode material for advanced electrochemical devices such as lithium-ion batteries and supercapacitors.