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 123.3 mAh g(-1) that can be delivered at 0.5 C rate as cathode and 128.4 mAh g(-1) that can be delivered at 0.2 Crate as anode. On this basis, a LNVP parallel to LNVP lithium ion full cell is fabricated, with an output output potential of similar to 2.48 V and a specific discharge capacity of 99.3 mA h g(-1). (C) 2014 Elsevier Ltd. All rights reserved.