The literature on the content and stability of vitamin C (ascorbic acid, AA) in citrus juices in relation to industrial practices is reviewed. The role of vitamin C from citrus juices in human diet is also reviewed. Citrus fruits and juices are rich in several types of bioactive compounds. Their antioxidant activity and related benefits derive not only from vitamin C but also from other phytochemicals, mainly flavonoids. During juice processing, temperature and oxygen are the main factors responsible for vitamin C losses. Non-thermal processed juices retain higher levels of vitamin C, but economic factors apparently delay the use of such methods in the citrus industry. Regarding packing material, vitamin C in fruit juice is quite stable when stored in metal or glass containers, whereas juice stored in plastic bottles has a much shorter shelf-life. The limiting step for vitamin C absorption in humans is transcellular active transport across the intestinal wall where AA may be oxidized to dehydroascorbic acid (DHAA), which is easily transported across the cell membrane and immediately reduced back to AA by two major pathways. AA bioavailability in the presence of flavonoids has yielded controversial results. Whereas flavonoids seem to inhibit intestinal absorption of AA, some studies have shown that AA in citrus extract was more available than synthetic ascorbic acid alone. DHAA is reported to possess equivalent biological activity to AA, so recent studies often consider the vitamin C activity in the diet as the sum of AA plus DHAA. However, this claimed equivalence should be carefully reexamined. Humans are one of the few species lacking the enzyme (L-gulonolactone oxidase, GLO) to convert glucose to vitamin C. It has been suggested that this is due to a mutation that provided a survival advantage to early primates, since GLO produces toxic H2O2. Furthermore, the high concentration of AA (and DHAA) in neural tissues could have been the key factor that caused primates (vertebrates with relative big brain) to lose the capacity to synthesize vitamin C. Oxidative damage has many pathological implications in human health, and AA may play a central role in maintaining the metabolic antioxidant response. The abundance of citrus juices in the Mediterranean diet may provide the main dietary source for natural vitamin C.