A novel biomass-based wood adhesive was prepared with commercial Mimosa tannin extract and glycerol diglycidyl ether (GDE) by convenient mechanical mixing. GDE served as the crosslinker of the tannin without any aldehyde addition yielding hardened three-dimensional networks. Different weight ratios of tannin/GDE were investigated by a number of techniques to determine their influence on final properties. The results showed that a non-hydrolysable ester bonds can be formed between the epoxy groups of GDE and hydroxyl groups of tannin, this being the critical factor for the good water resistance obtained by the wood adhesives prepared. Moreover, the dry and wet shear strength exhibit positive correlation with the proportion of GDE added. Even at a relatively small proportion of GDE (33% of the weight of dry tannin), the dry and 24 h cold water shear strengths of the bonded plywood satisfied the requirements of relevant standard (GB/T 9846-2015, ≥0.7 MPa). The thermal stability of the tannin-based wood adhesive so prepared progressively improved with the increasing proportion of GDE.