Pure PEG (p-PEG) and PEG/nano-Co
3O
4 (PEG/n-Co
3O
4) were pyrolyzed in helium atmosphere from 30 °C to 350 °C with heating rate of 20 °C/min, and the online volatile pyrolysis products were detected by a coupled gas chromatography/mass spectrometry (GC/MS). Seven series of products and four linear end groups (ethyl ether, vinyl ether, hydroxyl and methyl ether) from p-PEG pyrolysis were identified. Eight series of products from PEG/n-Co
3O
4 pyrolysis were identified, including four series with cycloether end group which was not detected from p-PEG pyrolysis. The end groups of the detected pyrolysis products, both linear and cycloether end groups, could be explained via free radical degradation decomposition pathway. The detected cycloether end group was considered to be derived from dehydrogenation and cyclization of a free radical resulted from C
![]()
O cleavage, with the existence of nano-Co
3O
4. The statistical results of the contents of the end groups showed that nano-Co
3O
4 reduced the probability of C
![]()
C cleavage comparing with C
![]()
O cleavage, and induced the hydrogenation of vinyl ether end group on its surface. The statistical results also confirmed the presumed approach of the cycloether end group forming.