Natural extracts, such as those from the residues of the Olea europaea industry, offer an opportunity for use due to their richness in antioxidant compounds. These compounds can be incorporated into porous polymeric devices with huge potential for tissue engineering such as bone, cardiovascular, osteogenesis, or neural applications using supercritical CO2. For this purpose, polymeric scaffolds of biodegradable poly(lactic-co-glycolic acid) (PLGA) and chitosan, generated in situ by foaming, were employed for the supercritical impregnation of ethanolic olive leaf extract (OLE). The influence of the presence of chitosan on porosity and interconnectivity in the scaffolds, both with and without impregnated extract, was studied. The scaffolds have been characterized by X-ray computed microtomography, scanning electron microscope, measurements of impregnated load, and antioxidant capacity. The expansion factor decreased as the chitosan content rose, which also occurred when OLE was used. Pore diameters varied, reducing from 0.19 mm in pure PLGA to 0.11 mm in the two experiments with the highest chitosan levels. The connectivity was analyzed, showing that in most instances, adding chitosan doubled the average number of connections, increasing it by a factor of 2.5. An experiment was also conducted to investigate the influence of key factors in the impregnation of the extract, such as pressure (10–30 MPa), temperature (308–328 K), and polymer ratio (1:1–9:1 PLGA/chitosan). Increased pressure facilitated increased OLE loading. The scaffolds were evaluated for antioxidant activity and demonstrated substantial oxidation inhibition (up to 82.5% under optimal conditions) and remarkable potential to combat oxidative stress-induced pathologies.