ABSTRACTThis contribution mainly studied the preparation of hyperbranched polyethylene (HBPE) fibers and HBPE/multiwalled carbon nanotube (MWCNT) composite fibers via electrospinning for the first time. Firstly, the effects of solvents, solution concentration, voltage, and rotating speed of collector on the morphology of HBPE fibers were studied. Among the factors, solvent type, concentration, and voltage showed notable influence on the morphology of HBPE fibers. HBPE has an excellent dispersion effect on CNT in organic solvents. Through ultrasonic dispersion, the HBPE solutions with dispersed MWCNT were obtained. Then HBPE/MWCNT composite fibers were obtained with different contents of MWCNT via electrospinning. The effects of voltage and working distance on the morphology of HBPE/MWCNT composite fibers were investigated. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42517.