Effects of fullerenes including FS, EFS and pure C60 on thermal behaviors of polyethylene glycol (PEG) have been studied by employing thermogravimetry-differential thermogravimetry (TG-DTG), differential scanning calorimeter (DSC) and off-line furnace-type pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). The products were collected by Cambridge filter pad which was widely used in analyzing the combustion products of cigarette. The results showed that the addition of fullerenes obviously restrained the thermal decomposition of PEG. The initial decomposition temperatures (IDT) and maximum decomposition peak temperatures (MDT) were evidently postponed by the addition of fullerenes. Pyrolysis products with one or two hydroxyl end groups obviously increased with the addition of 10% C60. The reasons of the changes were discussed from the aspects of reaction mechanisms.