Metal vanadium phosphates (MVP), particularly Li
3V 2(PO 4) 3(LVP) and Na 3V 2(PO 4) 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. In this work, a novel synthesis route for the preparation of LVP/NVP micro/mesoporous 3D foams via assembly of elastin-like polypeptides is demonstrated. The as-synthesized MVP 3D foams consist of microporous networks of mesoporous 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, with 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.