High molecular weight poly(N-vinyl carbazole) (PVCz) webs were obtained by the electrospinning technique. PVCz solutions were prepared by dissolving PVCz in chloroform and were spun under various electrospinning conditions. Especially, to improve the spinnability of PVCz, a high molecular weight specimen was adopted. Effects of processing parameters such as solution concentration, applied voltage, and tip–to-collector distance (TCD) on the spinnability, shape, and diameter and uniformity of fibres in the web were investigated. The average diameter of fibres in the webs was about 5 μm. The higher the solution concentration, the voltage, and the TCD, the finer and more uniform were the fibres in the web. PVCz fibres in webs prepared at high initial solution concentration were not cylindrical but planar, similar to “ribbons” but with nano-sized pores.