Sn ⁴⁺ in the LiSn₂(PO₄)₃ compound was doped with Cr ³⁺ ion. Single phase of α-LiSn₂(PO₄)₃ can be obtained with the Cr ³⁺ contents x=0.1-0.3 for the as-prepared Li_1+xCr_xSn_2-x(PO₄)₃ samples, which were confirmed by X-ray diffraction (XRD) measurement. Further augment of the Cr ³⁺ content led to the precipitation of a little secondary phase such as SnO₂. Although the introduction of Cr could not prevent the LiSn₂(PO₄)₃ from decomposition during initial discharging, the sample with Cr ³⁺ content of 0.3 showed remarkably enhanced electrochemical performances. Specific discharging capacities of 403.1 and 241.9 mAh/g could be delivered at current densities of 100 and 800 mA/g after 25 cycles, respectively. Improvement in electrochemical performance could be attributed to the steric effect of complex matrix composed of Li₃PO₄ and Cr, which was favorable for preventing Sn particles from aggregation during subsequent charge/discharge cycles, Leading to promote utilization efficiency of the precipitated Sn.