In this work, a multi-core-shell structured LiFePO4@Na3V2(PO4)3@C (LFP@NVP@C) composite is successfully designed and prepared to address inferior low-temperature performance of LiFePO4 cathode for lithium ion batteries. TEM confirms the inner NVP and outer carbon layers co-existed on the surface of LFP particle. When evaluated at low-temperature operation, LFP@NVP@C composite exhibits an evidently enhanced electrochemical performance in term of higher capacity and lower polarization, compared with LFP@C. Even at -10 oC with 0.5 C, LFP@NVP@C delivers a discharge capacity of ca. 96.9 mAh·g-1 and discharge voltage of ca. 3.3 V, which is attributed to the beneficial contribution of NVP coating. NASICON-structured NVP with an open framework for readily insertion/desertion of Li+ will effectively reduce the polarization for the electrochemical reactions of the designed LFP@NVP@C composite.