Organic/inorganic blend and self-crosslink reaction are elaborately incorporated to fabricate thermally stable and solvent resistant self-crosslinked TiO2/PAN hybrid membranes. This new fabrication method is a kind of mutual supporting technique which does not require a separate crosslinker or a catalyst. The prepared TPAN membrane shows excellent thermal stability which can persist up to 400 degrees C without any large mass loss and has good solvent resistance in various boiling systems including N,N-dimethylacetamide. The hybrid membrane also holds a very big BET surface area of 8.36 m(2)/g at 250 degrees C and can be successfully used as structured packing for distillation to separate IPA/water mixture. An extremely low mass transfer time 1/(K(G)a) of 0.1 s indicates that the hybrid membrane has excellent mass transfer performance. Similarly, for gas separation, because formed TiO2 can effectively reduce the pore size of membrane dense layer, the hybrid membrane also presents a good prospect in application under harsh environments. (C) 2014 Elsevier B.V. All rights reserved.