Peanut skin is a by-product rich in bioactive compounds with high nutritional and pharmaceutical values. The phenolic fraction, rich in proanthocyanidins/procyanidins, is a relevant class of bioactive compounds, which has been increasingly applied as functional ingredients for food and pharmaceutical applications and is mostly recovered from peanut skins through low-pressure extraction methods. Therefore, the use of green high-pressure extractions is an interesting alternative to value this peanut by-product. This review addresses the benefits of the phenolic fraction recovered from peanut skin, with a focus on proanthocyanin/procyanidin compounds, and discusses the improvement of their activity, bioavailability, and protection, by methods such as encapsulation. Different applications for the proanthocyanidins, in the food and pharmaceutical industries, are also explored. Additionally, high-pressure green extraction methods, combined with micro/nanoencapsulation, using wall material derived from peanut industrial processing, may represent a promising biorefinery strategy to improve the bioavailability of proanthocyanidins recovered from underutilized peanut skins.