The synthesis of a new biobased aromatic diisocyanate derived from lignocellulosic raw material, namely guaiacol and vanillyl alcohol, through phosgene-free routes offers the prospect of greener approaches for isocyanate production and the polyurethane industry. Indeed, bisguaiacol F diisocyanate (BGI) was obtained via a three-step process from readily available bisguaiacol F (BGF), involving conversion of aromatic amine into aromatic isocyanate. The unusual transition-metal-free conversion of BGF to bisguaiacol F diamine (BGA) was performed by a two-step approach: a) the Williamson-type alkylation of BGF and then b) the base-promoted Smiles rearrangement of bis O-Alkylated BGF. In order to improve the sustainability of this process, the first step was realized under solvent-free mechanochemical conditions, and the second step was performed using two different activating methods: thermal and microwave. The thermal process provided an isolated BGA yield of ca. 70%. Microwave activation proved to be an interesting alternative, although a lower yield (32%) of the desired BGA was achieved. Finally, the diisocyanate synthesis was performed via a phosgene-free/room temperature protocol using di-tert-butyl dicarbonate in presence of a catalytic amount of 4-dimethylaminopyridine (DMAP). Two polyurethane thermosets were designed and synthesized using the aromatic diisocyanates, biobased BGI and petrochemical-based methylene diphenyl diisocyanate (MDI), by a solvent-free two-step polymerization. Their thermo-chemical properties as well as their reactivities for polymer synthesis were evaluated. These preliminary results suggest that BGI could be potentially used as a nearly fully biobased surrogate for MDI.