In order to enhance the molecular orientation of electrospun nanofibers, a novel collection technique is proposed and applied to the spinning of polyethylene from high temperature solution. The technique makes use of a parallel-electrode collector that acts before solidification of the fiber occurs. The resulting multiple-necking morphology is composed of fine nanofibrils with very small diameter and narrow size distribution. The crystalline orientation of the nanofibrils was analyzed by TED. The formation mechanism of the nanofibrils is discussed. The strong elongational effect of the electric-field-induced stretching force in the parallel-electrode collector is demonstrated by the orientational analysis and by observation of the multiple-necking morphology.