We developed a temperature-controlled electrospinning apparatus specially for the polymers/IL system with high viscosity and surface tension and investigated the electrospinning of polyacrylonitrile (PAN)/1-butyl-3-methyl-imidazolium bromide ([BMIM][Br]) solutions. The rheological behaviors, surface tensions and conductivities of PAN/[BMIM]/[Br] solutions at different temperatures indicated that appropriately increasing the temperature is beneficial to their spinnability. It is also shown that PAN/[BMIM]/[Br] with a concentration of 3 wt%, 4 wt% and 5 wt% can be electrospun to fibers by increasing their temperatures to 70A degrees C, 75A degrees C or 85A degrees C, respectively. A rotating drum composed of a dacron mesh was used as a collector in order to avoid the contraction of the wet fibers. This present study provides an alternative method for electrospinning polymer fibers.