Pomegranate peels, which are normally processed as the main byproduct of pomegranate juice production, are worthy of being researched and utilized for the aim of economic and environmental benefits. In a phytochemical investigation of the peels of Punica granatum L., 10 phenolic compounds containing a common hexahydroxy diphenol moiety were isolated. Three of them were identified for the first time and named as pomegranatins A-C, and from the other seven known ones, two of them were obtained from pomegranate peels for the first time. Their structures were determined via extensive spectroscopic analysis. Besides, for the sake of preliminarily comprehending their biological activities, in vitro antimicrobial, antioxidant, as well as antitumor assays were detected. In the DPPH antioxidant assay, six compounds presented significant free radical scavenging ability. Two compounds exhibited moderate antimicrobial activities against Candida albicans; one compound could inhibit the proliferation of both C. albicans and Escherichia coli within limits. Four compounds possessed weak antitumor activity toward the Hela cell line without taking into account the bioavailability of ellagitannins. Overall, these results provided further information on the structural diversity of bioactive compounds present in pomegranate peels, as well as on their biological activities.