A series of LiNi0.5Mn1.5O4 cathode samples with different morphologies was synthesized via a template method and facile post-calcination process. Rod-like and truncated octahedral particles with {111} surface are obtained through increasing the calcination temperature. The exposed surface of as-prepared materials is mainly detected by SEM and TEM images. Detailed characterization of electrochemical performance of samples reflects that the T-775 cathode sample displays superior rate capability, and the discharge capacity reaches 108.2 mAh g−1 at 100C. The energy density of full cells, T-775 sample as the cathode material and commercial graphite as the anode material, retain 534.9 Wh kg−1 after 100 cycles. These improvements might be due to the synergistic effect of the {111} surface and smaller particle sizes, which improves interfacial stability and reduces the diffusion distance of Li+ during the interaction/deinteraction process.