This paper reports the dependence of conic angle of nanofibres on the processing and material parameters during electrospinning. Solutions of polyacrylonitrile (PAN) in dimethylformamide (DMF) with varied PAN concentrations were studied as the model systems, and they were electrospun into nanofibres at different high direct current (dc) voltages, flow rates and needle diameters. The dynamic and transient shear viscosities of the PAN/DMF solutions were characterized by a parallel-plate rheometer at varied shear rates. Rheological measurements showed that the PAN/DMF solutions behaved as Newtonian fluids at relatively low to medium shear rates, while the solutions with high PAN concentrations of 18 and 20 wt% exhibited a significant shear-thinning behaviour at high shear rates, especially in the case of transient shear mode. Experimental results indicated that at the electrostatic field of similar to 80 kV m(-1) and needle inner diameter of 0.48 mm (22 gauge), the conic angle of the nanofibre envelope decreased from similar to 160 degrees to similar to 75 degrees with an increase in PAN concentration from 12 to 20 wt%; at the PAN concentration of 16 wt%, the conic angle increased nonlinearly from similar to 40 degrees to similar to 160 degrees with an increase in electric field from 50 to 140 kV m(-1). In addition, experimental results showed that the needle inner diameter also noticeably influenced the conic angle. This study provided the experimental evidence useful for understanding the scaling properties of electrohydrodynamic jet motion for controllable electrospinning and process modelling.