Concerning the standstill state of pervaporation desulfurization, development of new pervaporation desulfurization membranes is vital. The polymer selection can be based on solubility parameter theory. Using group contribution method, the solubility parameter of poly[bis(trifluoroethoxy) phosphazene] (PTFEP) was calculated. The differences in solubility parameters between thiophene and polymers including PTFEP were calculated and investigated for their potential application as pervaporation desulfurization membranes. PTFEP had the most similar solubility parameter to thiophene among the polymers calculated in this work. The results indicated superior possibility for its application in pervaporation desulfurization. PTFEP was thus synthesized and characterized by DSC, GPC, XPS, H-1-NMR and P-31-NMR. The PTFEP composite membrane was fabricated and utilized in pervaporation removal of thiophene. A pretty high sulfur enrichment factor of 15.69 was obtained which confirmed the results suggested by the solubility parameter theory. Compared with literatures, we positively bet eve that an increase in solubility parameter differences causes a decrease in sulfur enrichment factor. Meanwhile, the swelling behavior and morphology of the membrane, the effect of feed temperature, and the effect of feed sulfur concentration were also investigated. (C) 2012 Elsevier BM. All rights reserved.