Electrospinning is a simple technique that has gained much attention because of its capability and feasibility in the fabrication of large quantities of fibers from polymer with diameters ranging in nano-microscale. These fibers provided high surface area to volume ratios, and it was of considerable interest for many applications, such as nanoparticle carriers in controlled release, scaffolds in tissue engineering, wound dressings, military wear with chemical and biological toxin-resistance, nanofibrous membranes or filters, and electronic sensors. Recently there has been a great deal of progress in the potential applications of hollow fibers in microfluids, photonics, and energy storage. In this work, electrospinning was conducted under high-pressure carbon dioxide (CO2) to reduce the viscosity of polymer solution. The experiments were conducted at 313 K and ~8.0 MPa. Polymer solution containing 5 wt% polymers which prepared in dichloromethane (DCM) with polyvinylpyrrolidone (PVP) to poly-L-lactic acid (PLLA) ratio 80:20 was used as a feed solution. The applied voltage was 15 kV and the distance of nozzle and collector was 8 cm. The morphology and structure of the fibers produced were observed using scanning electron microscopy (SEM). Under pressurized CO2, PVP electrospun was produced without bead formation with diameter ranges of 608.50 - 7943.19 nm. These behaviors hold the potential to considerably improve devolatilization electrospinning processes. © 2014 AIP Publishing LLC.