Fruit peels have a diverse range of phytochemicals including carotenoids, vitamins, dietary fibres, and phenolic compounds, some with remarkable antioxidant properties. Nevertheless, the comprehensive screening and characterization of the complex array of phenolic compounds in different fruit peels is limited. This study aimed to determine the polyphenol content and their antioxidant potential in twenty different fruit peel samples in an ethanolic extraction, including their comprehensive characterization and quantification using the LC-MS/MS and HPLC. The obtained results showed that the mango peel exhibited the highest phenolic content for TPC (27.51 ± 0.63 mg GAE/g) and TFC (1.75 ± 0.08 mg QE/g), while the TTC (9.01 ± 0.20 mg CE/g) was slightly higher in the avocado peel than mango peel (8.99 ± 0.13 mg CE/g). In terms of antioxidant potential, the grapefruit peel had the highest radical scavenging capacities for the DPPH (9.17 ± 0.19 mg AAE/g), ABTS (10.79 ± 0.56 mg AAE/g), ferric reducing capacity in FRAP (9.22 ± 0.25 mg AA/g), and total antioxidant capacity, TAC (8.77 ± 0.34 mg AAE/g) compared to other fruit peel samples. The application of LC-ESI-QTOF-MS/MS tentatively identified and characterized a total of 176 phenolics, including phenolic acids (49), flavonoids (86), lignans (11), stilbene (5) and other polyphenols (25) in all twenty peel samples. From HPLC-PDA quantification, the mango peel sample showed significantly higher phenolic content, particularly for phenolic acids (gallic acid, 14.5 ± 0.4 mg/g) and flavonoids (quercetin, 11.9 ± 0.4 mg/g), as compared to other fruit peel samples. These results highlight the importance of fruit peels as a potential source of polyphenols. This study provides supportive information for the utilization of different phenolic rich fruit peels as ingredients in food, feed, and nutraceutical products.