Exceptionally high specific capacities at ultrahigh charge/discharge currents have been obtained with a bi-material electrode prepared using Li3V1.95Ni0.05(PO4)3/C (LVNP/C) and activated carbon (AC) as coexisting active materials. Thanks to the amphoteric properties of LVNP/C, this electrode designated as LVNP/C-AC, has been evaluated both as positive and negative electrode in 1M LiPF6 in EC:DMC (1:1). At high specific currents (26.6Ag−1), the bi-material electrode delivers specific capacities as high as 61 and 24mAhg−1, between 3.0–4.3V and 3.0–1.5V vs Li/Li+, respectively. By contrast, the corresponding values for LVNP/C are 49 and 18mAhg−1. In both potential windows, the bi-material electrode shows an excellent cycling stability over 2000 cycles at 26.6Ag−1, with capacity retention of 95 and 89%, between 3.0–4.3 and 3.0–1.5V vs Li/Li+, respectively. The synergic effect of the activated carbon on the electrochemical performances of Li3V1.95Ni0.05(PO4)3/C is investigated by comparing the cyclic voltammetry, electrochemical impedance spectroscopy, electronic conductivity, galvanostatic cycling, and scanning electron microscopy of the bi-material electrode with the ones of LVNP/C. This study highlights the huge potentialities of this bi-material electrode for the development of high energy and high power Li-ion hybrid supercapacitors.