In this article, we report the syntheses and characterizations of a series of novel block polyelectrolytes, poly(styrene-block-sulfonated hydroxystyrene) (PS-b-sPHS), containing pendant sulfonic acid groups attached to the backbone via propyl spacers in the sPHS domain. PS-b-sPHS with various compositions were synthesized via anionic polymerization and the following analogous chemistry to achieve accurate control of molecular weight (M(w)), narrow polydispersity and high degree of sulfonation. Proton exchange membranes (PEMs) were prepared from PS-b-sPHS with sulfonic acids in either potassium salts or tetra-alkylammonium salts via solvent casting and following treatments. Some unique morphologies, such as hallow channels and lamellar arrangement of strings of beads, were observed as a consequence of equilibrium between microphase separation and columbic interactions between polyelectrolytes. The transportation properties were found to closely relate to the morphologies of the PEMs. The combination of microphase separation of block polyelectrolytes and freedom of movement of pendent alkylsulfonic acids was demonstrated to effectively enhance the proton transport and suppress the methanol crossover for the PEMs, leading to the selectivity higher than Nafion 117 by five times at most. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 2325-2338, 2011