Urea-formaldehyde resin was modified by a modifier with different synthetic processes labelled as UFM1, UFM2, and UFM3 respectively. As a comparison, normal UF resin with a F/U molar ratio of 1.1 labelled as UF0 was synthesized. The thermal behavior of modified urea-formaldehyde resins was studied by TG-DTA techniques, and the properties of plywood bonded with the UFM resins were investigated. The conclusions were as follows: (1) the modifier used in this study could significantly reduce the free formaldehyde content of urea-formaldehyde resin and the formaldehyde emission of plywood; (2) The exothermic peak temperatures of DTA curve were 129.37, 125.05, 120.98, and 116.11 °C for UF0, UFM1, UFM2, and UFM3 respectively. (3) The plywood manufactured with UFM2 and UFM3 resins have high bonding strength (1.28MPa and 1.59MPa) and low formaldehyde emission value (E1 grade).