This paper describes our work on the synthesis of a series of sulfonated homo-/co-polyimides (SPI) which were obtained by post-sulfonation method over three steps. In the first step, 4,4'-oxydianiline (ODA) and 4,4'-diaminodiphenylsulfone (DDS) dissolved in N-methyl pyrrolidone (NMP) were reacted with benzophenonetetracarboxylic dianhydride (BTDA) in order to yield poly(amic acid) (PAA). Secondly, precipitated PAA was sulfonated via concentrated sulfuric acid (95-98%) at room temperature to give post-sulfonated PAA (PSPAA). Finally, PSPAA was converted into post-sulfonated PI (PSPI) by the thermal imidization method. PSPIs with ion exchange capacity (IEC) ranging from 0.20 to 0.67meq/g were prepared. The thermal properties of the PSPIs were evaluated and high desulfonation temperature was found in the range of 190-350 degrees C, suggesting the high stability of sulfonic acid groups. In water, PSPI-5 membrane displayed similar proton conductivity to Nafion (R) 117, whereas this membrane showed poor conductivity in dry state. All PSPIs displayed good solubility in common polar aprotic solvents such as NMP and dimethylacetamide (DMAc). Furthermore, the effects of post-sulfonation reaction on chemical structure, thermal oxidative behavior, and physical properties of the PSPI membranes such as membrane quality/stability and water uptake were discussed. (c) Copyright 2008 John Wiley & Sons, Ltd.