Membrane-based separation processes are receiving increasing attention in the scientific community and industry since they provide a desirable alternative to processes that are not easy to achieve by conventional separation technologies. In particular, gas separation using polymeric membranes have annually grown so fast owing to advantages such as easy installation, no moving parts, small footprint and low energy process. The key element is definitely a polymer membrane exhibiting high permeability and high selectivity to compete with other gas separation technologies. Current polymer membranes used for commercial gas separation are a family of hydrocarbon polymers for hydrogen separation, air separation and carbon dioxide separation from natural gas sweetening. Relatively, gas or vapor separation properties of fluoropolymers are not known so much as compared with those of hydrocarbon polymers. Accordingly, in this study, membranes prepared from amorphous perfluoropolymers are of particular interest because of the unique properties of these polymers. The advantages offered by these amorphous perfluoropolymers for use in gas and vapor separation will be discussed. In addition, membrane properties and separation performance will be compared with other membranes available on the market.