For increasing the curing rate and decreasing the curing temperature, modified phenol-formaldehyde (PF) resins were synthesized under a complex catalyst. The bonding strength and formaldehyde emission of the plywood bonded by them were measured according to Chinese National Standards methods. The curing behavior was conducted by differential scanning calorimetry (DSC) measurement. The results indicate that PF resins catalyzed by the complex catalyst show more moderate pH values, lower curing temperature and shorter gel time comparing with control ones. Plywood bonded with modified PF resins shows good bonding strength and low formaldehyde emission even at low hot press temperature (110 °C), which is closed to the plywood bonded with normal control PF resin at high hot press temperature (130 °C).