Poly (ethylene chlorotrifluoroethylene) (ECTFE) membrane presents interesting properties for microfiltration (MF) and membrane distillation (MD). In this paper, ECTFE is prepared via thermally induced phase separation (TIPS) process using acetyl tributyl citrate (ATBC) as an environmentally friendly diluent. Phase diagram of the ECTFE/ ATBC system is measured, and the effects of ECTFE concentration and quenching bath temperature on the membrane structure, properties and performance are investigated, by characterizing with scanning electron microscope (SEM), pure water flux, contact angle, mechanical properties, mean pore size and porosity. The results show that the ECTFE membranes prepared with ATBC as diluent possessed spherulite structure, high hydrophobicity and liquid entry pressure of water (LERw), promising permeate flux, salt rejection and mechanical strength in vacuum membrane distillation (VMD). The permeate flux reached to 22.3 L/(m(2).h) with salt rejection rate of 99.9%. These results indicated that EC1 FE membranes prepared with green diluent ATBC is an interesting candidate for VMD operation.