High cut-off voltage in lithium ion batteries (LIBs), now, is the vital threshold for further development of high energy density LIBs. In this work, the NASICON type solid electrolyte as high working voltage and unique ionic transfer rate material is introduced to facilitate the high cut-off performance of Ni-rich cathode material. Herein, considering the uniformity of coating outer layer, the charge attraction is employed as a coating method to form a homogeneous coating layer. The coating properties of LiTi2(PO4)3 coated LiNi0.6Co0.2Mn0.2O2 probed via X-ray diffraction, scanning electron microscope, transmission electron microscope, X-ray photoelectron spectroscopy. Typically, electrochemical tests show that LiTi2(PO4)3 was effectively promoting the electrochemical characters. The modified material preserves 94% after 100 cycles at 1C in voltage of 2.7–4.3 V. Especially, it maintains 92.3%/83.6% in high cut-off voltage of 2.7–4.5 V/2.7–4.8 V for 100 cycles, and keeps 117.4 mA h g−1/101.2 mA h g−1 after 500 long cycles.