The pomegranate (Punica granatum L.) market has steadily grown due to the increasing demand of health-conscious consumers of products with health-promoting effects. Recently, a growing interest in developing ecological and environmentally friendly extraction methods has led to investigating extraction procedures to obtain a higher extraction yield using a lower amount of solvents and energy. Herein, a new extraction procedure was developed to obtain an enriched pomegranate food supplement by using the peels of pomegranate, cultivar “Dente di Cavallo” and its juice. The extraction was performed through a non-conventional extraction technique like SLDE-Naviglio using ethanol and pomegranate juice as a solvent, and peels as a matrix. The extract was analysed by a combined approach based on LCESI/QExactive/MS/MS and NMR analysis, and its chemical profile was compared with those of pomegranate juice and of the extract obtained from peels by SLDE-Naviglio by using ethanol:H2O. The LC-MS analysis highlighted the presence of hydrolysable tannins, flavonoids, ellagic acid and phenol glucoside derivatives, while 1H NMR analysis completed the profile by detecting the primary metabolites. The LC-MS and 1H NMR analysis indicated that the extract obtained by SLDE-Naviglio using ethanol and pomegranate juice was enriched in the bioactives as confirmed by the highest phenolic, tannin and flavonoid content.