Electro-osmotic effect in a porous medium arises from the electrically charged double layer at the fluid-solid interface, whereby an externally applied electric field can give rise to fluid flow. The electro-osmotic pump (EOP) is potentially useful for a variety of engineering and biorelated applications, but its generally low efficiency is a negative factor in this regard. A study to determine the optimal efficiency of the EOP and the condition(s) under which it can be realized is therefore of scientific interest and practical importance. We present the results of a theoretical and experimental study on the maximum efficiency optimization of the electrokinetic effect in artificially fabricated porous media with controlled pore diameters. It is shown that whereas the EOP efficiency increases with decreasing channel diameter, from 4.5 to 2.5 μm for samples fabricated on oxidized silicon wafers as expected for the interfacial nature of the electro-osmotic effect, the opposite trend was observed for samples with much smaller channel diameters fabricated on anodized aluminum oxide films, with the pore surface coated with silica. These results are in agreement with the theoretical prediction, based on the competition between interfacial area and the no-slip flow boundary condition, that an optimal efficiency of ~1% is attained at a microchannel diameter that is five times the Debye length, with a zeta potential of ~100 mV.