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Metal vanadium phosphates (MVP), particularly Li3V2(PO4)3 (LVP) and Na3V2(PO4)3 (NVP), are regarded as the next-generation cathode materials in lithium/sodium ion batteries. These materials possess desirable properties such as high stability, theoretical capacity and operating voltages. Yet, low electrical/ionic conductivities of LVP and NVP have limited their applications in demanding devices such as electric vehicles (EVs). In this work, a novel synthesis route for the preparation of LVP/NVP micro/meso-porous 3D foams via assembly of elastin-like polypeptides is demonstrated. The as-synthesized MVP 3D foams consist of micro-porous networks of meso-porous nanofibers, where the surfaces of individual fibers are covered with MVP nanocrystallites. TEM images further reveal that LVP/NVP nanoparticles are about 100 200 nm in diameter each particle enveloped by a 5 nm thick carbon shell. The MVP 3D foams prepared in this work exhibit ultrafast rate capabilities (79 mA h g-1 at 100C and 66 mA h g-1 at 200C for LVP 3D foams; 73 mA h g-1 at 100C and 51 mA h g-1 at 200C for NVP 3D foams) and excellent cycle performance (almost 100% performance retention after 1000 cycles at 100C); their properties are far superior compared to current state-of-the-art active materials.