Resol-type phenolic resin (RPR)/polyvinylalcohol(PVA) blends were prepared and the effect of RPR/PVA blend ratio on the thermal properties of the blends was investigated with differential scanning calorimeter (DSC) thermogravimetric analysis (TGA) techniques. The intermolecular interaction between RPR and PVA was confirmed by Fourier transform infrared (FT-IR) spectroscopy. Cure activation energy ($E_{a}$) and glass transition temperature ($T_{g}$) were obtained by DSC analysis. TGA results were also used to calculate initial decomposition temperature (IDT), integral procedural decomposition temperauture (IPDT), and decomposed activation energy. FT-IR results show the presence of hydrogen bonding in the polymer blends. $E_{a}$ shows a maximum value when PVA content is 5 vol%. ALL the DSC thermograms of different phenolic blend systems in the second scan exhibit a single $T_{g}$, indicating that the phenolic blend systems are miscible. Also, TGA results show that thermal stability is best when PVA content is 5 vol%, which is in good agreement with the $E_{a}$ results. This is probably due to the intermolecular hydrogen bonding interaction between the hydroxyl groups in RPR and PVA.