A series of polybenzimidazoles (PBIs) with different main chains and sulfonated PBI were successfully synthesized from the corresponding dicarboxylic acids and 3,3'-diaminobenzidine for the formation of ultrathin, single-component, and semipermeable membranes. Furthermore, the covalently crosslinked PBI membrane was prepared by the reaction of sulfonated PBI with divinyl sulfone. Their water transport properties were evaluated under a reverse osmosis mode and compared with the primary structure based on the water permeability (A) and salt permeability (B) values normalized by the membrane thickness. It was found that the A and B values of the PBIs were improved with increasing the weight ratio of the imidazole rings per repeating unit, the introduction of sulfonate group as the hydrophilic group to the PBI was an effective way to enhance the A value, and the crosslinked structure enhanced the salt rejection rate (R) value while maintaining the water flux.