Microfluidic vanadium redox fuel cells are membraneless and catalyst-free fuel cells comprising a microfluidic channel network with two porous carbon electrodes. The anolyte and catholyte for fuel cell operation are V(II) and V(V) in sulfuric acid based aqueous solution. In the present work, the electrochemical characteristics of the vanadium redox reactions are investigated on commonly used porous carbon paper electrodes and compared to a standard solid graphite electrode as baseline. Half-cell electrochemical impedance spectroscopy is applied to measure the overall ohmic resistance and resistivity of the electrodes. Kinetic parameters for both V(II) and V(V) discharging reactions are extracted from Tafel plots and compared for the different electrodes. Cyclic voltammetry techniques reveal that the redox reactions are irreversible and that the magnitudes of peak current density vary significantly for each electrode. The obtained kinetic parameters for the carbon paper are implemented into a numerical simulation and the results show a good agreement with measured polarization curves from operation of a microfluidic vanadium redox fuel cell employing the same material as flow-through porous electrodes. Recommendations for microfluidic fuel cell design and operation are provided based on the measured trends. (C) 2012 Elsevier Ltd. All rights reserved.