Redox flow batteries represent a remarkable alternative for grid-scale energy storage. They commonly employ carbon felts or carbon papers, which suffer from low activity towards the redox reactions involved, leading to poor performance. Here we propose the use of electrospun freestanding carbon materials derived from lignin as alternative sustainable electrodes for all-vanadium flow batteries. The lignin-derived carbon electrospun mats exhibited a higher activity towards the VO2 +/VO2+ reaction than commercial carbon papers when tested in a three-electrode electrochemical cell (or half-cell), which we attribute to the higher surface area and higher amount of oxygen functional groups at the surface. The electrospun carbon electrodes also showed performance comparable to commercial carbon papers, when tested in a full cell configuration. The modification of the surface chemistry with the addition of phosphorous produced different effect in both samples, which needs further investigation. This work demonstrates for the first time the application of sustainably produced electrospun lignin-derived carbon electrodes in a redox flow cell, with comparable performance to commercial materials and establishes the great potential of biomass-derived carbons in energy devices.