Mass transport properties of electrodes prepared from graphite felt, as such and after silicification, have been studied using cyclic voltammetry. Within the graphite felt, the mass transport of a probe changes with decreasing scan rate, from a radial diffusion around fibers to a regime that is analogous to “thin-layer” systems. Furthermore, unlike classical “thin-layer” systems, the volume comprised in the felt is macroscopic (resulting in high current densities), while the time required to consume all diffusive species remains in the 1 min range. Silicification of graphite felt does not impact on the mass transport of the negatively charged molecular probe Fe(CN)63– but significantly slows mass transport of positively charged Ru(NH3)63+. In the latter case, a parallel decrease of peak current intensity reflects limited mobility of the probe due to its strong interaction with the surface of the pore walls. These data provide important information for the optimization of the working conditions of these electrodes for the design of biosensors and biofuel cells.