Thermally induced phase separation (TIPS) process is an important method to prepare high performance poly(vinylidene fluoride) (PVDF) membranes, but the toxic diluent for membrane formation poses environmental problems. In the present paper, Methylene glycol diacetate (TEGDA) was introduced as a low toxic diluent to fabricate PVDF membranes via TIPS method. A specific fibrillar structure which yields the PVDF membranes with high elongation and permeability was formed. Morphologies, structures, properties and permeation performances of the PVDF membranes showed that they presented alpha phase, narrow and unimodal pore size distribution, bicontinuous and fibrillar structure, good mechanical strength and comparable permeability. (C) 2014 Elsevier B.V All rights reserved.