Four kinds of biorefinery residues (the ethanol, the butanol, the xylitol and the lactic acid biorefinery residue) were utilized to modify the phenol–formaldehyde (PF) resin, respectively by copolymerization. Prior to the reaction, the composition and functional group of each biorefinery residue were characterized and used to evaluate their suitability as replacement for the preparation of PF resins. It was found that ER (bio-ethanol biorefinery residue) exhibited high reactivity due to high content of hydroxyl group. The influence of each biorefinery residue for the replacement of phenol on the properties of residue-modified phenol formaldehyde (RPF) resins was also investigated using Fourier transform infrared spectroscopy (FT-IR), solid state 13C NMR and thermo gravimetric analyzer (TGA). ER was found to be the best biorefinery residue for the modification of PF resin. 50% phenol could be replaced by ER without influencing the properties of adhesives and plywoods. In industrial production, the plywoods bonded by ER-derived PF resins met the requirement of both first grade and E0 grade (GB/T 9846.3-2004).