Chemical and sensorial changes related to the use of benzoates and ascorbic acid as additives in packed fermented vegetables were investigated. For this, three selected vegetables (green olives, cucumbers, and caperberries) stored under different conditions (glass or plastic containers, ambient or refrigerated storage) were used. In all cases, benzoic acid remained unchanged (glass bottle) or decreased slightly (plastic pouch) at prolonged storage. Ascorbic acid was partially or totally degraded during storage, the degradation rate depending on the storage conditions and the vegetable matrix. Benzene levels higher than 10 μg/L were found in cucumbers and caperberries containing both additives, but only when packed in plastic pouches and after prolonged storage at room temperature. In these conditions, an appreciable browning of brine, related to AA degradation, was also found. The use of benzoate alone had a significant influence on vegetable color, but flavor was not significantly affected at the benzoate levels tested. On the basis of the present study, benzoates should be removed from fermented vegetable formulations containing ascorbic acid to eliminate possible benzene formation during long-term storage.