Chili pepper fruits are important sources of bioactive compounds e.g., capsaicinoids, carotenoids, ascorbic acid, flavonoids, phenolic compounds, and minerals. From them, chili pepper fruits synthesize and accumulate important concentrations of ascorbic acid (AsA) (also known as vitamin C). AsA has an important role as a free-radical scavenger and as an effective antioxidant. In plants, AsA develops crucial functions for the homeostasis maintenance of the cells, whereas, in animals, AsA is very important for cellular metabolism too. Because of humans and some animal species are incapable of synthesizing AsA, they must acquire it from vegetable food, and chili pepper fruits represent an excellent option for vitamin C uptake. In this review, we integrate the latest biological advances of the research about vitamin C in chili pepper fruits including biosynthesis, accumulation, and the effects of agricultural practices and postharvest storage.