Chitosan was added to PVA aqueous solutions as a thickener to improve the electrospinning process. The presence of a small amount of chitosan considerably improved the uniformity of as-spun nanofibres. This improvement is attributed to its significant effect on the solution viscosity and conductivity, with only a slight impact on the surface tension. The concentration of the PVA required to produce bead-free and uniform nanofibres was reduced with the increase in chitosan concentration. The chitosan thickener suppressed the jet break-up and facilitated the jet stretching so that fine and uniform fibres could be electrospun even from a dilute PVA solution.