The fatigue fracture behavior of chlor-alkali monolayer membranes is investigated under a condition similar to the membrane electrolysis cell service environment, i.e., at 86°C in brine solution. The linear elastic fracture mechanics (LEFM) approach, i.e., da/dN vs. AK, is implemented in this study. It is found that the fatigue crack propagation behavior of the chlor-alkali membranes can be successfully characterized via the LEFM technique. The fatigue fracture surfaces of the membranes are also investigated using stereo-optical microscopy and are found to show typical fatigue striation patterns. Detailed experimental procedures for preparing and testing of the membranes are presented.