A series of ether-bond free polybenzimidazole (PBI) bearing pendant imidazolium groups (HIm-PBI and PIm-PBI) are synthesized via a low cost preparation process under mild reaction conditions. HIm-PBI and PIm-PBI show excellent membrane forming property, and flexible HIm-PBI- and PIm-PBI-based membranes are prepared by casting the polymer/dimethyl sulfoxide solution. For a comparison, ether-bond free PBI without pendant imidazolium groups (I-PBI) was synthesized and characterized in detail, and I-PBI shows poor membrane forming ability under the...