Green composite fibers (339-612 nm in diameter) have been developed from wood pulp, acetylated wood pulp and polyethylene oxide under various concentrations by electrospinning process. A polymer solution concentration of 7 wt% with 5 wt% wood pulp have been found to produce uniform composite fibers. Scanning electron microscopy micro-images demonstrated that composite fibers diameter and morphology depended on the processing parameters, such as solution concentration and molecular weight of polymer. Transmission electron microscopy and laser confocal microscopy observations indicated that the acetylated wood was well dispersed and oriented along the length of composite fibers axis. X-ray diffraction studies revealed that the structure of electrospun composite fibers became more non-crystalline.