Near-infrared light sources have potential applications in many fields. Cr3+ is a good luminescence centre to prepare near-infrared phosphors. Improving the performance of existing near-infrared luminescent materials has indeed attracted great interest from researchers. The luminescence properties of Zn2TiO4:Cr3+ were improved by crystal field engineering strategies. Zn2+-Ti4+ was partially replaced using a Li+-Nb5+ ion pair based on the Zn2TiO4:Cr3+ phosphors. Luminescence Cr3+-activated luminescent materials are sensitive to changes in the local crystal structure and crystal field environment. Doping of Li+-Nb5+ increased the luminescence intensity up to 2.7 times that of the undoped sample. Also, the thermal stability of the phosphor was greatly increased by the replacement of Li+-Nb5+.