The Vesuvian Piennolo cherry tomato (Lycopersicon esculentum Miller) (PdP) is an old and typical variety grown in the Campania region (Italy). PdP is referred to as a long-storage tomato due to its thick and coriaceous skin that allows long post-harvest storage and it has been granted Protected Designation of Origin (PDO) status since 2009. In this study, the chemical composition, focusing in particular on organic acids, antioxidant molecules and volatile compounds, were investigated in PdP and compared to another typical variety in Campania, the Ciliegino tomato (CIL). Chemical characterization was evaluated for both the CIL and PdP varieties during storage in the same environmental conditions until deterioration of 50% of the fruits; deterioration occurred in PdP after 6 months and in CIL tomatoes after 1 month. The results demonstrated variation in the chemical profiles of both varieties with storage length. Particularly, the PdP variety appears richer in antioxidants compounds (i.e., chlorogenic acids and lycopene) and organic acids (i.e., glutamic and malic acids) than does CIL. Additionally, both varieties display different profiles of volatile bioactive compounds and they are differently influenced by the storage time. The results indicate a typical chemical composition of this long-storage tomato closely linked to the geographic origin area.