The growing demand for low cost carbon fibers for mainstream composite applications has driven recent interests in using lignin as alternative choice of material for carbon fiber precursor. Lignin, a highly aromatic, plant-derived amorphous polymer has been considered as potential carbon fiber precursor but often encounters issues in spinning fine fibers for carbonization. Copolymers of polyacrylonitrile/lignin have been identified as an alternative precursor for spinning raw fibres using conventional solution spinning technique. This work is focused on studying the influence of esterification of lignin prior to copolymerization on the properties of lignin/ polyacrylonitrile copolymers. Lignin/polyacrylonitrile copolymers were successfully synthesized and verified using FT-IR and NMR characterization techniques. The thermal properties of the copolymers were studied by DSC and TGA analysis.