Phenol-urea-formaldehyde cocondensed (PUF) resins of high urea content were prepared by adding different forms of urea to the reaction system. The structure, curing behavior, and water resistance of the PUF resins were investigated, and their relations were also discussed by liquid (13)C nuclear magnetic resonance (NMR) and different scanning calorimetry (DSC). The liquid (13)C-NMR analysis showed that urea added in the form of methylolureas was well incorporated into the cocondensed resins by reacting with phenolic methylols to form cocondensed methylene bridges, and that the PUF resins had no free formaldehyde with any form. Unreacted urea and low molecule monosubstituted urea of PUF resins play a dominant role in the curing behavior and water resistance of resins. The peak temperature, curing time, and curing enthalpy (Delta H) value correspondingly increased, however, the water resistance of PUF resins decreased when urea content in PUF resins increased. The PUF cocondensed resin with up to 89.4 % (W(U)/W(P)) urea has relatively low cost, and moreover can pass the requirements of China Industry Standard for the exterior grade of structural plywood after 4-h cyclic boiling test. (C) Koninklijke Brill NV, Leiden, 2009