Poly(vinylidene fluoride)/sulfonated poly (phthalazinone ether sulfone ketone) (PVdF/SPPESK) blend membranes are successfully prepared by solution blending method for novel proton exchange membrane (PEM). PVdF crystallinity, FTIR-ATR spectroscopy, thermal stability, morphology, water uptake, dimension stability, and proton conductivity are investigated on PVdF/SPPESK blends with different PVdF contents. XRD and DSC analysis reveal that the PVdF crystallinity in the blends depends on PVdF content. The FTIR-ATR spectra indicate that SPPESK remains proton-conducting function in the blends due to the intactness of -SO3H group. Thermal analysis results show a very high thermal stability (T-d1 = 246-261 degrees C) of the blends. PVdF crystallinity and morphology study demonstrate that with lower PVdF content, PVdF are very compatible with SPPESK. Also, with lower PVdF content, PVdF/SPPESK blends possess high water uptake, e.g., P/S 10/90 and P/S 15/85 have water uptake of 135 and 99% at 95 degrees C, respectively. The blend membranes also have good dimension stability because the swelling ratios are at a fairly low level (e.g., 8-22%, 80 degrees C). PVdF/SPPESK blends with low PVdF content exhibit very high proton conductivity, e.g., at 80 degrees C, P/S 15/85 and P/S 10/90 reach 2.6 x 10(-2) and 3.6 x 10(-2) S cm(-1), respectively, which are close to or even higher than that (3.4 x 10(-2) S cm(-1)) of Nafion115 under the same test condition. All above properties indicate that the PVdF/SPPESK blend membranes (particularly, with 10-20% of PVdF content) are very promising for use in PEM field. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 116: 852-860, 2010