The olive oil industry produces large volumes of wastes, which are also potential sources of bioactive compounds by developing healthy and/or functional foods. Extraction of phenolic compounds from the residues of the olive oil is mainly carried out with solvents. However, there is currently a growing public awareness about the use of organic solvents in food processing, which has pointed out the need for the application of clean technologies such as pressurized liquid extraction (PLE). Therefore, the aim of this research was to optimize the phenolic compound extraction from olive pomace by PLE, establishing the qualitative and quantitative phenolic profile by HPLC-ESI-TOF/MS. The extraction design to recover phenolics from olive pomace demonstrates a great compositional variability of PLE extracts obtained under different experimental conditions. Indeed, quantitative results have pointed out the selectivity of PLE extraction when this technique is applied to the treatment of olive pomace. PLE-optimized conditions showed higher total phenolic compound content than conventional extraction (1659 mg/kg d.w. and 281.7 mg/kg d.w., respectively). Among these phenolics, the quantity of secoiridoids and flavonoids in the optimized PLE extract was three and four times higher than in conventional extracts. Furthermore, optimal PLE conditions allowed to obtain an enriched hydroxytyrosol extract which was not detected in the conventional one.