Through orthogonal experimental methods, the melt electrospinning of pure phenolic fibers has been achieved. The preparation is based on an orthogonal experimental method, which was designed to investigate the optimal conditions for production through integrated effects of spinning temperature, gap between spinneret and collector, as well as applied voltage. We found that optimal spinning conditions at 160 degrees C, a spinneret-to-collector gap of 8 cm, and applied voltage at 40 kV produce an average electrospun fiber diameter reaching 4.44 +/- 0.76 m, with narrow variance distribution. The fibers were cured in a solution with 18.5% formaldehyde and 12% hydrochloric acid, heated from room temperature to 80 degrees C and maintained 1h. In this report, the morphology, structural changes, and heat resistance of the fibers are characterized. Obtained results reveal that curing the fiber reduces crystallization and improves heat resistance. (c) 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42574.