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Cayenne pepper is high in vitamin A. It also contains vitamin B6, vitamin E, vitamin C, riboflavin, potassium and manganese. More importantly it is a good source-( most peppers are)- for capsicum, which is beneficial for a number of ailments including; cancer, weight loss & arthritis.
Red Bell Peppers are a great source of vitamin C, containing more vitamin C than green bell peppers and almost 4 times as much as an orange bell pepper.
Peppers of the genus Capsicum, including cayenne pepper and red bell peppers, contain around 1.0 mg of vitamin C per gram (yes, there are variations among species and cultivars). The question is that although you can easely eat 100 g of bell peppers, and thus ingest more vitamin C than you need in a day, I doubt you can do the same with a species that has a Scoville rate between 30,000-50,000, like Cayenne pepper.
In conclusion, although they do have vitamin C in reasonable concentrations, the nutrional value of peppers in what concerns this nutrient is not that high due to the usually low amounts ingested.