High performance hybrid phase Li2NaV2(PO4)3 (H-LNVP) composite consist of rhombohedral Li3V2(PO4)3 (60.9%), rhombohedral Na3V2(PO4)3 (31.6%) and monoclinic Li3V2(PO4)3 (7.5%) is successfully synthesized via a sol-gel method. The rhombohedral phase Li2NaV2(PO4)3 (R-LNVP) is also obtained for comparison. The H-LNVP delivers better electrochemical performance, higher Li+ diffusion coefficient and more stable structure than that of R-LNVP duo to the existence of small amount monoclinic Li3V2(PO4)3. For the synthesised H-LNVP, there are 123.3mAhg-1 that can be delivered at 0.5C rate as cathode and 128.4mAhg-1 that can be delivered at 0.2Crate as anode. On this basis, a LNVP||LNVP lithium ion full cell is fabricated, with an output output potential of ∼2.48V and a specific discharge capacity of 99.3mA hg−1.