The thermal degradation of phenol-formaldehyde resins (PFR)was studied using thermogravimetry analysis (TG) technique. The structural changes of thermal degradation of synthetical and commercial PFR were investigated by Fourier-transform infrared rays (FTIR) and solid-state C-13 nuclear magnetic resonance (C-13 NMR) spectroscopy. The experimental results show that the degradation of PFR can be divided into three stages. Additional cross-links are formed and small exposed groups of the cured resin are removed in the first stage. In the second stage, methylene bridges decompose into methyl groups then both phenol and cresol homolog appear. The degradation of phenol group occurs in the third stage. According to these results, a novel degradation mechanism of phenol-formaldehyde type resins is proposed: the mainly degradation process of PFR is the decomposition reaction of methylene bridges in this mechanism instead of auto-oxidation of the methylene bridges in the prevenient mechanism. (C) 2008 Published by Elsevier B.V.