The reaction of a desulphurized kraft lignin with hexamethylene diamine as a model of a polyamine has been investigated. For this purpose, guaiacol was also used as a lignin model compound and treated under similar conditions. Solid state CP-MAS 13C NMR, FTIR and MALDI-TOF spectroscopy studies revealed that polycondensation compounds leading to resins were obtained by the reaction of the amines with the phenolic and aliphatic hydroxy groups of lignin. Simultaneously a second reaction leading to the formation of ionic bonds between the same groups occurred. These new reactions have been clearly shown to involve several phenolic and alcohol hydroxyl groups, as well as lignin units oligomerization, to form hardened resins