This work aimed to evaluate the influence of the aliphatic and aromatic hydroxyl level on the polyurethane adhesive property and chemical structure. This adhesive was obtained through the reaction of technical Kraft lignin (TKL) as polyol with diphenylmethane diisocyanate (MDI). Thus, lignopolyurethane adhesives were obtained with NCO: OH ratios of 0.8: 1.0, 0.9: 1.0, 1.0: 1.0, 1.1: 1.0, and 1.2: 1.0. Initially only the TKL aliphatic hydroxyl level was taken into consideration in the stoichiometry in order to define the mass ratio between MDI and polyol. Subsequently, lignopolyurethane adhesive was obtained using the same NCO: OH ratios considering TKL total hydroxyls' level, and aromatic and aliphatic hydroxyls. The chemical structures of the synthesized adhesives were analyzed by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (C-13 NMR). The mechanical property of the adhesively bonded joints, comprising wood substrates and synthesized adhesives, was measured using single lap shear tests. Results illustrated that by increasing the NCO: OH ratio, there is an increase in the free isocyanate content leading to higher shear strength values. Higher free isocyanate content leads to MDI dimer formation in the lignopolyurethane structure.