Novel epoxy-based semi-interpenetrating polymer networks (semi-IPNs) of aromatic polyimide, derived from 2,2-benzidinedisulfonic acid (BDSA), were prepared through a thermal imidization reaction. Dynamic scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR) were utilized to verify the synchronization of the imidization of sulfonated poly(amic acid) (SPAA) and the crosslinking reactions of epoxy. The semi-IPNs of epoxy/sulfonated polyimides (SPI-EPX) exhibit excellent film-forming characteristics and mechanical integrity at room temperature. Conductivities at 100 degrees C of 0.0243 S cm(-1) (SPI-EP30) and 0.0141 S cm(-1) (SPI-EP50) were obtained, which are similar to that of the Nafion 117 (0.0287 S cm(-1)). The increase in the conductivity of SPI-EP(30,40) with temperature is more rapid than that of Nafion 117. The SPI-EPX exhibited lower methanol permeability than did Nafion 117. The hydrolytic stability of the SPI-EPX was followed by FTIR spectroscopy at regular intervals. SPI-EPX prepared using epoxy-based semi-IPNs of sulfonated polyimide, SPI-EP(40,50), exhibited higher hydrolytic stability than the phthalic polyimides (five-membered ring polyimides). The microstructure was analyzed using atomic force microscopy (AFM) in the tapping mode, which demonstrated that SPI-EP50 exhibited a nanophase that was separated into an essentially reticulated and venous hydrophobic and hydrophilic domains. Transmission electron microscopy (TEM) confirmed widespread and well-connected hydrophilic domains, proving the higher hydrolytic stability and strong proton-transporting properties of the SPI-EPX membrane. (c) 2008 Wiley Periodicals, Inc.