Gas transport of helium, hydrogen, oxygen, nitrogen, methane, and carbon dioxide gases in a series of polyarylates based on isophthalic acid has been examined. These polyarylates were prepared from bisphenol A, hexafluorobisphenol A, phenolphthalein, and fluorene bisphenol monomers to study the effects of varying the bisphenol connector group size and shape. Substitution of a tertiary butyl group at position five on the isophthalate ring increases polymer permeability. The incorporation of a large, bulky connector group increases gas permeability and maintains permselectivity while the substitution of t-butyl groups increases gas permeability by two- to fourfold but lowers permselectivity. Most of the increases in permeability can be related to increases in the diffusion coefficients of all the gases. All the polyarylates have high glass transition temperatures and may be suitable for high temperature gas separation applications.