A rotating wheel was used as the collector during electrospinning to produce aligned nanofiber. Then the effects of wheel rotating speed and LiCl (Lithium Chloride) additives on nanofiber morphology and mechanical behavior of nanofiber mat were studied. The results indicated that the rotating speed of 150 rpm (round per minute) was desirable for fabricating well-aligned nanofiber with nanoscale diameter. Fiber diameter and fiber angle both showed exponential relationship with wheel rotating speed. Meanwhile fiber assemblage was observed when 0.4, 0.6 or 0.8 wt% LiCl was added in 12 wt% polyacrylonitrile (PAN) with N,N-dimethylformamide solution respectively. LiCl adding increased nanofiber diameter but had not obviously influence on fiber angle. The mechanical examination revealed that LiCl adding decreased the stress of PAN mats and 0.6 wt% LiCl was appropriate for desirable stress and strain. The failure stress and failure strain of the PAN mat with 0.6 wt% LiCl was 50.23 MPa and 82.45%, respectively. POLYM. ENG. SCI., 51:2178-2183, 2011. (C) 2011 Society of Plastics Engineers