Polymer electrolyte membrane fuel cells are considered as an ideal candidate to replace the internal combustion engines in cars and trucks. The use of Nafion membranes in the fuel cell can limit the efficiency performance when the cell temperature is above 85°C. Here, we review a preparation method and structure-property- performance relationship of a polybenzimidazoles (PBI) membrane. Unlike Nafion membranes, PBI-based membrane can be operated at high temperature and low relative humidity. © 2016 Scrivener Publishing LLC. All rights reserved.