Sulfonated poly(ether ether ketone) copolymers (SPEEK) with a range of sulfonate contents (SC 77-51%) were synthesized via nucleophilic substitution polycondensation from hydroquinone and sulfonated hydroquinone. Membranes obtained by solvent casting from dimethylacetamide onto glass surfaces were analyzed for surface behavior. The surfaces of a membrane were hydrophobic in air, but hydrophilic in water. This surface behavior was corroborated by water contact angle vs. time, using sessile drop measurements. Hydrophilic sulfonic group aggregates on SPEEK chain and various media contacting with the top or bottom surfaces of the membrane during the fabrication process caused differences in surface behavior. Angle-dependent XPS showed that there was a higher atomic S/C ratio of the bottom surface than on the corresponding top surface. The hydrophilic sulfonic groups were in higher concentration within the membrane, with the concentration gradually decreasing towards the surface for SPEEK-HQ-80 and SPEEK-HQ-70 membranes. Acidification with strong acid and higher temperature induced a more hydrophilic surface on a membrane than a milder acidification process. The depth profile at the membrane surface was examined by a combination of contact angle, XPS and ATR-FTIR.