This article is a study of the feasibility of electrochemically separating hydrogen from hydrogen/ethylene mixtures. Experimental results are presented for the performance of the anode of a proton exchange membrane (PEM) fuel cell that is used to separate hydrogen/ethylene mixtures. Experiments were performed using a single cell PEM fuel cell. The experimental results show that, to a large extent, the ethylene reacts with the hydrogen in the anode chamber to form ethane. in spite of this reaction, it is still possible to separate a significant portion of the hydrogen and options for improving the separation efficiency are discussed. A zero-dimensional mathematical model of the hydrogen separation and hydrogenation process has been developed and it has been shown that this model gives generally good agreement with the experimental results. (C) 2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.