The compatibility between dimethyl methylphosphonate (DMMP)-based electrolyte of 1M LiPF6/EC+DMC+DMMP (1:1:2wt.) and spinel materials Li4Ti5O12 and LiNi0.5Mn1.5O4 was reviewed, respectively. The cell performance and impedance of 3-V LiNi0.5Mn1.5O4/Li4Ti5O12 lithium-ion cell with the DMMP-based nonflammable electrolyte was compared with the baseline electrolyte of 1M LiPF6/EC+DMC (1:1wt.). The nonflammable DMMP-based electrolyte exhibited good compatibility with spinel Li4Ti5O12 anode and high-voltage LiNi0.5Mn1.5O4 cathode, and acceptable cycling performance in the LiNi0.5Mn1.5O4/Li4Ti5O12 full-cell, except for the higher impedance than that in the baseline electrolyte. All of the results disclosed that the 3V LiNi0.5Mn1.5O4/Li4Ti5O12 lithium-ion battery was a promising choice for the nonflammable DMMP-based electrolyte.