Nowadays, there is a growing interest in botanicals for human nutrition and care. Arbutus unedo wild berries are edible and medicinal fruits that contain many healthy bioactive components, which can be considered a valuable resource for the food ingredient market and for nutraceutical and cosmetic sectors. In the present study, the polyphenols and in vitro antiradical and hypoglycemic activities of five wild Italian accessions of A. unedo were investigated, and their chemical profiles were treated by means of unsupervised chemometric techniques like the hierarchical and principal component analysis. Moreover, Fourier-transformed mid-infrared spectroscopy was used to provide a rapid assessment of the phytochemical composition of different accessions. Samples differed mainly in their anthocyanin content and overall nutraceutical potential. Anthocyanins were present mainly as glycosides of cyanidin and delphinidin, with delphinidin-3-O-glucoside being the most abundant one, ranging from 49 ± 1 to 111 ± 3 mg g−1 (for P1 and P2, respectively; p < 0.05). Extracts were screened for their in vitro biological activities by using the 2,2′-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) (ABTS•+), 2,2-diphenyl-1-picrylhydrazyl (DPPH•) antiradical tests, while their hypoglycemic activity was investigated by the α-glucosidase inhibition test. In both in vitro antiradical tests, the highest capacity was recorded for P2 (EC50: 1.17 and 0.064 mg mL−1, for DPPH• and ABTS•+, respectively), with values higher than those reported in the literature for A. unedo fruit extracts. P2 also showed the highest inhibition power towards α-glucosidase (about 70%). Moreover, the nonparametric correlation analysis pointed out a very high significant correlation between the percentage of α-glucosidase inhibition and cyanidin-3-O-rutinoside (r: 0.973; p < 0.01). Finally, the application of hierarchical analysis to samples analyzed provided three different clusters based on the average phytochemical content coded as low, medium and high. Moreover, principal component analysis made it possible to establish similarities among the accessions depending on their overall nutraceutical characteristics and on the relative anthocyanin content.