This study is aimed at understanding the limits in reducing the size of a membrane-based CO2 separator and its pressure head needs and energy consumption, while maximizing its selectivity. The separator consists of a flow channel capped by a hydrophobic nanoporous membrane through which CO2 exits the anode flow stream of a direct methanol fuel cell (DMFC). A systematic study is conducted to determine the effect of differential pressure across the membrane, flow velocity, and flow channel dimensions on the separation process. The extraction flux was found to change linearly with pressure difference across the membrane, The effect of flow velocity on the extraction flux was negligible up to a critical velocity beyond which the separation process ceased. The separation selectivity enhanced by increasing the differential pressure across the membrane but did not change with varying the flow velocity and channel depth. Using the findings of the first part of the study, an optimal micro-separator (with a footprint of approximately 10 x 1 mm(2)) was designed/fabricated for a 20 W DMFC and its performance was experimentally analyzed. An unprecedented separation selectivity of close to 200 was achieved at a differential pressure of about 10 kPa and negligible energy consumption. Published by Elsevier B.V.