Novel macro and meso porous polysulfone materials were prepared from miscible blends of polysulfones with a phenylindane containing polyimide by selective chemical decomposition of the polyimide phase using a dilute hydrazine or tetraammonium hydroxide solution in methanol. It was found that the pore size of the material is affected by the backbone structure of the polysulfone selected. The compatibility between the polysulfones and the polyimide is influenced by the polysulfone structure. This in turn affects the pore size and the pore size distribution of the final porous material. Polyether sulfone was found to form most compatible blends that in turn leads to a porous material with the smallest pore size, a meso porous material. The meso porous polyether sulfones are transparent films, with uniform pore sizes in the range of 30 nm, while bisphenol A polysulfone based porous materials are opaque with pore sizes in the range of 200 nm. (C) 2009 Elsevier Ltd. All rights reserved.