Larch tannin, a valuable forest product resource, offers the benefits of being natural, renewable and environmentally friendly. With growing environmental concerns, the widespread use of phenolic resins in the wood industry has been limited due to the depletion of fossil resources and formaldehyde emission issues. In this study, larch tannin was modified using a NaOH/urea solution to enhance phenolic resin properties. The curing properties and thermal stability of the adhesives were analyzed using a differential scanning calorimeter (DSC) and thermogravimetric analysis (TGA), and the formaldehyde emissions were also measured. The results showed that this treatment effectively reduced the resin’s gel time. LTPF-U-4 resin demonstrated the highest bonding strength of 1.09 MPa and exhibited low formaldehyde emissions, thereby meeting the requirements for Class I plywood (≥0.7 MPa) and complying with the E0 grade of plywood standards as outlined in the China National Standard GB GB/T 17657-2013. The sodium hydroxide/urea-treated larch tannin substitution improved the bonding performance of the LTPF-U resins; its impact on bonding strength is limited. Nevertheless, the treatment significantly reduces the formaldehyde emissions of plywood bonded with LTPF-U resins. The NaOH/urea treatment not only reduced the thermal stability of the resin but also improved its curing properties and lowered its curing temperature. This research offers valuable insights for developing modified phenolic resins, which have significant practical implications.