The effects of solvents such as 1,1,2,2-tetrachloroethane (TCE) and tetrahydrofuran (THF) and other processing parameters of electrospinning on the spinnability of high molecular weight poly(N-vinyl carbazole) (PVCz) solution and morphological variations of the as-spun PVCz web were investigated. That is, electrospun PVCz webs with various dimensions and shapes were obtained by controlling the type and amount of solvent and processing parameters like applied voltage, tip to the collector distance, and solution concentration. In the cases of all parameters, the average diameter of fibres in PVCz web electrospun in TCE was finer than that in THF. In addition, minimum diameters of fibres were about 900 nm and 3 μm for TCE and THF, respectively. In THF, PVCz fibres at high initial polymer concentration were not cylindrical but planar, which were similar with “ribbon” and nano-sized pores, resulting from the differences in evaporation rates and in the viscosities of the solvent and the solutions.