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Modification of sulfonated poly(ether ether ketone) (SPEEK) membrane was attempted by blending three newly developed charged surface modifying macromolecules (cSMMs) having three different polyols. Sulfur content of the cSMMs was analyzed by Fourier transform infra-red spectroscopy and elemental analysis to be in the following order: PEG200-HBS>PEG400-HBS>PPG-HBS, which was also the order for their glass transition temperature (T_g). The control and modified membranes were characterized by contact angle measurement, thermal analysis, X-ray photoelectron spectroscopy, atomic force microscopy and water uptake. The modified SPEEK membrane surfaces were more hydrophilic on the top surfaces than the bottom surfaces as indicated by the water contact angle and by XPS, confirming the stronger migration of cSMM to the top than the bottom surfaces. The cSMM has migrated and formed SO₃ …