Formaldehyde has widely been used for the cross-linking of polyvinyl alcohol polyvinyl alcohol polymer. The effects of formaldehyde on the water resistance of MDF cement composites were investigated as a function of types of catalyst, base or acid, and the amount of formaldehyde. The acetalization, reaction of OH group of PVA with aldehyde, was ended incompletely under base atmosphere. However, by addition of citric acid, the cross-linking of PVA polymer could be acheved through acetalization of PVA and formaldehyde. The effects of these different patterne according to the types of catalyst on the water resistance of MDF cement were studied by the preparation of PVA films and MDF composites. Thanks to the cross-linking reaction of PVA polymer chains by formaldehyde, the modified PVA films and MDF composites showed a good water-resistant propety. The modified MDF cement composite to which 3 wt% formaldehyde and 1 wt% cirtic acid were added showed 80% of initial flexural strength and good interfacial state between cement grain and polymer matrix. However, 4 wt% formaldehyde deteriorted the processing conditions, microstructures and eventually the flexural strength, causing sharp increase in the viscosity of sample dough during the mixing process. To study the relatins of flexural strength and interface of cement grain and polymer matrix, SEM and MIP measurement were performed.