This paper reports an eco-friendly approach of extracting cellulose acetate (CA) from waste cigarette filter to construct cellulose based membrane separator for high-performance lithium ion battery. Cellulose/PVDF-HFP nanofiber membrane was prepared by a co-axial electrospinning of cellulose acetate core and PVDF-HFP shell, then hydrolyzed by LiOH. The cellulose-core/PVD-HFP-shell fibrous membrane shows good tensile strength (34.1 MPa), high porosity (66%), excellent thermal stability (to 200 °C) and super electrolyte compatibility (355% electrolyte uptake). It has a lower interfacial resistance (98.5 Ω) and higher ionic conductivity (6.16 mScm-1) than those of commercial separator (280.0 Ω and 0.88 mScm-1). In addition, the rate capability (138 mAh61g-1) and cycling performance (75.4 % after 100 cycles) are also superior to those of the commercial separators, demonstrating cellulose-core fibrous membrane to be a promising separator for high-power and more secure lithium-ion battery.