Novel lignin-chitosan polyelectrolyte fibres were produced through a reactive electrospinning process. Polyelectrolyte formation between the anionic lignin and cationic chitosan was controlled through the pH of the solution. Through manipulating the polyelectrolyte complex formation, fibres could be effectively produced from two biopolymers, which are normally very difficult to electrospin on their own. Though minimal amounts of the petroleum-derived polyethylene oxide were introduced into the solution to enhance the spinnability of the polyelectrolyte solution, it could be easily removed from the fibres post spinning by washing with water. Thus, pure biopolymer fibres could be produced. The optimum composition of lignin to chitosan was identified through SEM, FTIR and TGA analysis of the electrospun fibres. Fluorescence spectra of the electrospun fibres reveal the homogeneous distribution of lignin and chitosan components throughout the fibre network.