Electrospinning is a versatile process used to prepare micro- and nano-sized fibers from various polymers dissolved in volatile solvents. In this report, cellulose and cellulose-heparin composite fibers are prepared from nonvolatile room temperature ionic liquid (RTIL) solvents by electrospinning. RTILs are extracted from the biopolymer fiber after the fiber formation using a cosolvent. Micron to nanometer sized, branched fibers were obtained from 10% (w/w) concentration of polysaccharide biopolymer in RTIL solution with an applied voltage of 15-20 kV. Cellulose-heparin composite fibers showed anticoagulant activity, demonstrating that the bioactivity of heparin remained unaffected even on exposure to a high voltage involved in electrospinning.