The objective of the present research work was to develop a membrane with a high H2O/alcohol selectivity for pervaporation and for use in direct alcohol fuel cells. Sulfonated poly (ether ether ketone) (SPEEK) was coated with a thin continuous carbon molecular sieve (CMS) layer. The membranes obtained had 180- and 400-nm thick CMS layers that led to a clear reduction of alcohol crossover. The water/alcohol selectivity increased with the size of the alcohol molecules as follows: methanol < ethanol < n-propanol < iso-propanol. A water/n-propanol selectivity of up to 34,000 was obtained, confirming the molecular sieving effect. The system was tested in a direct methanol fuel cell using standard electrodes, and demonstrated a better performance than with plain membranes. In a later stage Pt was introduced in the CMS layer during the preparation of the membrane electrode assemblies, this had the advantage that the CMS layer not only acted as an alcohol barrier but also as a catalyst support.