Synthesis and characterization of the novel sulfonated BAPPO monomer and its use in the synthesis of a new phosphine oxide-based sulfonated polyimide are described. BTDA, 6FDA, and DDS were used as monomers in the polyimide synthesis. Sulfonated polyimide membranes were obtained by a solution thermal imidization method. The thermal behavior of the polymers was investigated by DSC and TGA. The morphological structure of the membranes was investigated by tapping-mode AFM. The proton conductivities of the sulfonated polyimide increased regularly as a function of sulfonated diamine content. The conductivities are good compared to typical proton exchange membranes.