Perfluorosulfonate ionomer membranes (PFSIs) were cast from Nafion((R)) propanol-water solutions of varying equivalent weights (950, 1100, and 1200 Da) and all annealed at 100 degreesC under vacuum. Sulfonate group surface concentration on the various membranes and its effect on the adsorption of a cationic polyacrylamide were investigated utilizing X-ray photoelectron spectroscopy (XPS). The cationic polyacrylamide is employed in the microelectronics industry for electroless printed circuit fabrication and may be used to pattern electrodes directly onto the PFSI surfaces for fuel cell miniaturization. Sulfonate surface concentration was found to be well correlated to the sulfonate bulk concentration obtained from the known equivalent weights of the Nafion((R)) solutions. Adsorbed cationic polyacrylamide surface coverage was found to be independent of the immersion time in the adsorbate solution. A wide variation in adsorbate coverage (from 0 to 60% of the surface) occurred over a comparatively small variation in the sulfonate repeat unit surface concentration (from 0 to 20% of the total Nafion((R)) repeat units). Adsorbate coverage goes through a maximum as the sulfonate concentration increases and is consistent with a random, enthalpy-driven adsorption process. Greater sulfonate concentration and lower associated adsorbate coverage was detected on cast membranes than previously found with commercially prepared membranes. (C) 2002 Elsevier Science Ltd. All rights reserved.