An aluminophosphate adhesive was used as the binder in plywood. The hot-pressing parameters of aluminophosphate adhesive-based plywood (APPs) including hot-press temperature (A), time (B), and pressure (C) were optimized using response surface methodology. Results indicated that the hot-press temperature was the most dominant factor. The maximum bonding strength of 1.98 MPa was found with an optimal parameter of 171 °C (hot-press temperature), 7.5 min (hot-press time), and 1.0 MPa (hot-press pressure). Additionally, the chemical reaction mechanism between aluminophosphate adhesive and wood fibers was characterized by X-ray photoelectron spectroscopy (XPS). Results showed that good interaction was generated between wood fibers and adhesives through their surface functional groups. In conclusion, the optimized pressing conditions of plywood significantly improved bonding strength of APPs.