Polybenzimidazolium hydroxides are of potential interest for the use in alkaline anion exchange membrane fuel cells (AAEMFC). Introduction of an ether group in para-position of the 2-phenyl substituent improves the mesomeric stabilization of imidazolium cations, and O-PBI seems to be more stable than meta-PBI under alkaline conditions. NMR, IR and XPS analysis show a structural change when the iodide form is exchanged into the hydroxide form. Surprisingly, this structural change is subject to a pH sensitive equilibrium and the pure imidazolium form is retained immediately when the pH is lowered. The molecular structure at high pH is either the 2-carbinol or the amine-amide. Further hydrolysis necessitates excess hydroxide.