The wettability, bonding strength and flexibility of modified melamine–urea–formaldehyde resin adhesive with hydroxymethyl lignin (LMUF) were investigated. Moreover, the curing performance, thermal properties and chemical structure of LMUF were analyzed by differential scanning calorimetry (DSC), thermogravimetry (TG), scanning electronmicroscopy (SEM), X–ray diffraction (XRD), Fourier–transform infrared spectroscopy (FTIR) and 13C nuclear magnetic resonance (13C–NMR). The synthesis mechanism of LMUF was also discussed. The results demonstrated that: (1) LMUF resin is characterized by low free formaldehyde and a short pot life. (2) With the increase in hydroxymethyl lignin, the bonding strength and flexibility of the LMUF increased first and then decreased. They reached their maximum when the hydroxymethyl lignin content was 6%–8%, which represented increases of 36% and 102%, respectively. (3) The DSC and TG analyses showed that the LMUF resin had a high hot-pressing temperature, but its thermostability was increased. (4) The XRD and SEM analyses proved that the LMUF resin was characterized by flexibility failure, especially at 6% of hydroxymethyl lignin. (5) Hydroxymethyl lignin is a type of flexible long-chain molecule, which was introduced into spaces between the rigid triazine rings through adhesion and penetration, thus improving the regular single structural form of MUF resin and increasing the compactness of the system. As a result, the resin had stronger deformability and cohesion in the molecules. The bonding strength and flexibility were improved to different degrees.