The global mass transfer and the local flow structure inside a set of crossing minichannels were characterized using the electrodiffusion method. The individual square-cross channel sections (a = 1.5 mm in sides) intersect at right-angles in order to form the flow cell. An array of 39 circular platinum electrodes (0.25 mm in diameter) was flush-mounted into the wall of the flow cell to investigate the wall shear rate at different locations. This array of small sensors allowed characterization of longitudinal and lateral variations in wall shear rate across the flow cell, flow distribution at the inlet and outlet sections, transition between laminar and turbulent flow regimes, and flow behaviour at the channel crossings. The results of global wall mass transfer measurements demonstrated that, from a mass transfer point of view, the flow cell exhibits similar behaviour to a porous medium.