Several compositional parameters (fatty acids, tocopherols, polar phenols and volatiles) in virgin olive oils from varieties located at the center of Tunisia, namely Baldi, Chemchali, Neb Jmel, Tounsi and Besbessi from Gafsa and Chemchali and Sehli cultivated in Sidi Bouzid, were studied. To the best of our knowledge, this is the first study focusing on the chemical composition of virgin olive oils (VOO) from Sidi Bouzid. Significant differences were found between varieties from Sidi Bouzid and Gafsa in monounsaturated saturated fatty acid levels, some volatile compounds and γ-tocopherol amounts. Notably, Tounsi and Baldi VOOs showed the highest six carbon atoms alcohol contents, whereas Neb Jmel VOO revealed the highest aldehyde six carbon atoms content. Fatty acid composition, as well as tocopherol content, showed differences among different VOO. Principal component analysis and hierarchical component analysis on polar phenols, fatty acids, tocopherols and volatiles data evidenced a good discrimination among oils from the different investigated varieties.