Electrochemical performance of spinel LiNi0.5Mn1.5O4 (LNMO) at elevated temperature is improved by solid-state electrolyte Li2O–Al2O3–TiO2–P2O5 (LATP) coating. Crystallinity and thickness of coatings are controlled by adjusting the coating process at two different temperatures (550 and 650 °C). 2.0 wt.% LATP-modified LNMO cathode materials obtained at 650 °C exhibits remarkably promoted electrochemical performance compared to that of the pristine one in terms of cycling and rate ability at 55 °C. The enhanced performance of the surface-modified samples can be accounted for the suppressed side reactions between the cathode materials and electrolyte solution. What is more important is that LATP cannot only protect the active materials from electrolyte solution but also improve Li+ mobility. The higher crystallinity of glass-ceramic LATP coating layer with thinner thickness implies more unobstructed, stable and shorter diffusion path of Li+ transport. It is found that the coating process is in favor of the disordered to ordered phase transition, implying that the heating process of coating plays a role of anneal as well.