Octahedral cathode materials LiNi0.5Mn1.5O4 (LNMO), with primary particles size of 300–600 nm are prepared through one-step co-precipitation. Then solid-state electrolyte Li2O-Al2O3-TiO2-P2O5 (LATP) was coated on LNMO to form continuous surface-modification layer. There is no obviously difference of structure, morphology between coated LATP LiNi0.5Mn1.5O4 (LATP-LNMO) and pristine LiNi0.5Mn1.5O4 (P-LNMO). Low-temperature electrochemical performance of P-LNMO and LATP-LNMO electrodes, including charge-discharge capacity, cycle performance, middle discharge voltage and electrochemical impedance spectra (EIS), were measured systematically with three electrode. The results reveal that LATP-LNMO electrode presents superior electrochemical performance at low temperature, compared to P-LNMO electrode. At −20 °C, the capacity retention of LATP-LNMO (61%) is much higher than that of P-LNMO (39%). According to EIS, the enhancement of performance of LATP-LNMO cathode at low temperature can be attribute to LATP coating, which not only promotes lithium-ion diffusion at electrode/electrolyte interface but also decreases the charge transfer resistance. Finally, the electrochemical performances of full cell of LATP-LNMO or P-LNMO cathode vs Li4Ti5O12 anode are investigated. The energy density can be achieved to 270 Wh·Kg−1 at −20 °C if using LATP-LNMO, which is much better than that of P-LNMO.