We report a new discovery for enhancing Li ion transport at the surface of Li3V2(PO4)3 particles through superionic pathways built along an ionic conductor. The Li3V1.95Zr0.05(PO4)3/C composite has much higher initial discharge capacity, superior rate-capability, and excellent cycling performance when compared with pristine Li3V2(PO4)3/C. This is partly due to the occupation of vanadium sites by Zr4+ ions in the Li3V2(PO4)3 host crystals and facile Li ion migration through a LiZr2(PO4)3-like secondary phase that forms on the surface of the Li3V1.95Zr0.05(PO4)3 particles. Our findings about high Li ion transport and structure stabilization induced by Zr incorporation suggests a breakthrough strategy for achieving high-power Li rechargeable batteries using NASICON-structured cathode materials in combination with nanoarchitecture tailoring.