The purpose of the study was to manufacture water-resistance plywood with using UF resin modified by emulsifiable polyisocyanate. The emulsifiable polyisocyanate which contains plenty of hydrophilic segments and teminal isocyanate groups were synthesized by reaction between various kinds of polyether polyols and polymeric methane dipthenyl diisocyanate (pMDI). A type of composite adhesive was obtained from the mixture of emulsifiable polyisocyanate and urea formaldehyde resin. The process parameters, such as the molar ratio of –NCO and –OH, mass fraction of emulsifiable polyisocyanate in UF resin and accessory ingredient have a great influence on the composite adhesive. X-ray photoelectron spectroscopy (XPS) had been used to analyze the chemical structure of bonding interface. The results showed that the composite adhesive consisting of UF resin and emulsifiable polyisocyanate content of 7.5% and kaolin content of 1.5% was used in plywood with high physical and mechanical properties, water resistance and low formaldehyde emission.