The effect of surface property of LiNi1/3Co1/3Mn1/3O2 on the low temperature performance is seldom studied. Herein, the trace Ti surface-doped LiNi1/3Co1/3Mn1/3O2 exhibits enhanced discharge capacity under low temperature. After doping, the discharge capacity of LiNi1/3Co1/3Mn1/3O2 at −20 °C is 51.3 mAh g−1 at 5C, which is near twice as much as the bare material (30.1 mAh g−1). Via the X-ray diffraction, scanning electron microscope, energy dispersive spectroscopy and X-ray photoelectron spectroscopy analysis, it is confirmed that Ti doping on the surface significantly alters the surface property of LiNi1/3Co1/3Mn1/3O2 particle. The surface-doped Ti efficiently changes the lattice parameters, reduces the electrochemical reaction resistance and finally enhances the discharge capacity. The study clarifies the nature of trace Ti surface doping and is helpful for understanding the enhancement mechanism of the low temperature performance of LiNi1/3Co1/3Mn1/3O2.