The apple is a food rich in diverse classes of polyphenols (PP), among which the proanthocyanidins (PCs), which are primarily concentrated in the skin, are one of the most abundant. These compounds are of considerable interest for their possible positive health effects because of their antioxidant properties. However, depending on the classes of PP present (chemical composition) and their relative concentrations in the apple skin, their antioxidant effects vary and some of their components can even generate prooxidant effects. This work determined the chemical composition and antioxidant-prooxidant potential of a polyphenolic extract (PPE) and a proanthocyanidin-rich fraction (PRF) of apple skin, along with the contribution of their most abundant individual compounds, based on their copper chelating ability, ease in reducing peroxidase-generated free radicals and TEAC (Trolox-Equivalent Antioxidant Capacity) assay. For this purpose, chromatographic and colorimetric methods were used. The majority compounds identified in PPE were flavan-3-ols (44.58%), flavonols (42.89%) and dihydrochalcones (11.60%). In PRF, we detected monomers and oligomers from dimers to heptamers, which were composed of 97% (−)-epicatechin and 3% (+)-catechin. The antioxidant potential was notably higher in PRF than in PPE. The (−)-epicatechin monomer and the procyanidin B2 dimer showed more ease in reducing peroxidase-generated free radicals compared to other compounds of the apple skin, whereas phloridzin dihydrochalcone produced prooxidant effects.