Structural and morphological control is an effective approach for improvement of electrochemical performance in rechargeable batteries. In this paper, three different morphological Na3V2(PO4)3 (irregular shaped, the porous sponge-like and plate like) were successfully prepared through controlling the amount of oxalic acid by a simple two-step reduction method. It is found that the amount of oxalic acid has vital impacts on the morphology of Na3V2(PO4)3; moreover, the morphological evolution and formation mechanism are proposed based on the reactions of different amount of oxalic acid occurring in the two-step reduction process. The excellent electrochemical performances of the porous sponge-like Na3V2(PO4)3 are attributed to the unique morphology. The initial capacity of the porous sponge-like Na3V2(PO4)3 is 101.77 mAh g−1 at 30 C; after 700 cycles, it remains as high as 89.28 mAh g−1 with only 12% capacity loss. When the current density increases to 50 C and 70 C, the capacity retentions of 81% after 600 cycles, and 92.5% after 500 cycles are achieved, respectively.