Blend hydrophilic polyamide imide (PAI)-sulfonated poly (ether ether keton) (SPEEK) hollow fiber membranes were fabricated for oil-water emulsion separation. The structure and performance of the membranes were examined by FESEM analysis, N2 permeation, overall porosity, collapsing pressure, water contact angle, pure water flux, molecular weight cutoff (MWCO), and oil rejection tests. By studying ternary phase diagrams of polymer/solvent-additive/water system, the higher phase-inversion rate was confirmed for the solutions prepared at higher PAI/SPEEK ratio. A more open structure with larger finger-likes was observed by increasing PAI/SPEEK ratio. Mean pore size of 81 nm, overall porosity of 79% and water contact angle of 58° were obtained for the improved membrane prepared by PAI/SPEEK ratio of 85/15. Increasing SPEEK ratio resulted in lower mechanical stability in terms of collapsing pressure. Pure water flux of about 2.5 times of the plain PAI membrane was found for the improved membrane. MWCO of 460 kDa was found for the improved blend membrane. From oil rejection test, all the membranes demonstrated an oil rejection of over 95%. The improved membrane showed a lower rate of permeate flux reduction compared to the plain membrane which was related to the smaller fouling possibility. Less fouling resistance of the improved membrane was related to the higher flux recovery ratio (about 92%). For all the membranes, the dominant fouling mechanism was found to be the cake filtration. The improved PAI-SPEEK hollow fiber membranes was found to be practical for ultrafiltration of oily wastewaters.