In this study, the renewable resource valonea (Quecus acutissima Carr) tannin (VT) was used to partially replace phenol in the production of a phenol-tannin-formaldehyde (PTF) resin by batch polymerization. The chemical structure of VT was characterized using Fourier transform infrared spectrum (FTIR) and 13C nuclear magnetic resonance (13C NMR). Matrix-assisted laser desorption/ionization-time of flight mass spectrometry (MALDI-TOF-MS) and solid state 13C NMR were used to explore the chemical structure of the PTF resin. The characterization showed that VT was mainly composed of galloyl groups, hexahydroxydiphenol groups and glucose. Moreover, it was evident that a copolycondensation reaction occurred between phenol, VT and formaldehyde, where these species crosslinked with one another through methylene bridges. The performance of plywood bonded with the novel PTF resin was also investigated. The test results showed that the VT-modified PF resin had suitable viscosity and low quantities of free formaldehyde. Furthermore, the bond strength of the plywood bonded using the PTF resin met the Chinese National Standard (GB/T 9846.3–2004). Moreover, the formaldehyde emission met the requirement of ASTM D6007-02 for CARB level (≤0.08 ppm). Therefore, it was concluded that VT could be a promising natural resource for partial replacement of phenol in the manufacture of phenol-formaldehyde resin for the plywood industry.Graphical Abstract: