Carotenoids are highly unsaturated natural pigments and health-promoting compounds susceptible to oxidative degradation during food processing and storage. Despite the recognized negative consequences of carotenoid degradation, the mechanisms involved are not well elucidated. The objective of this study was to evaluate the oxidative degradation of β-carotene in a model system. The model system was prepared by adsorbing β-carotene, isolated from sweet potato by open column chromatography, in microcrystalline cellulose (1 mg of β-carotene/g of dry powder). The volatile compounds were captured using the technique of solid phase microextraction (SPME). About 1 g of the model system was placed in a 20 mL flask, which was immediately sealed with PTFE septum, after flushing with oxygen during 5 minutes. The flasks were placed horizontally in the oven at 32°C or 60°C for 24 hours. The headspace volatile compounds were captured using a mixed fiber DVB/CAR/PDMS. Identification was performed by gas chromatography-mass spectrometry (GC/MS) and by comparison of the experimental and literature Kovats indices. The peak areas of the volatiles formed were intensified at 60°C. Major short acyclic compounds were identified as 2,4-heptadiene, 2,6-dimethyl and 5-hepten-2-one, 6-methyl; considering their chemical structures, they apparently came from the polyene chain. Epoxy β-ionone, possibly coming from cleaved β-ionone ring, was also identified.