Membranes techniques used to convert chemical energy into electrical energy from energy sources such as hydrogen, salt water, and water. Membrane materials have transport property of desire molecular and barrier property for satisfy to requirement of cell performance. Typically, PFSA polymer is used to fabricate membrane. Each material has different characteristics depending on the membrane formation conditions. Macroscopic characteristics are difficult to correlation with molecular motion, mobility, and transport within membrane matrices. NMR spectroscopy can analysis about these characteristics by observing the molecule level. In this study, NMR spectroscopy can provide fundamental information of PFSA ionomers and correlation with macroscopic characteristics.