Low density Polyethylene (designated hereafter as “PE”) is known for its inactivity, durability and resistance to degradation. For this reason adding pro-oxidants as additives in PE matrix could be efficient to elaborate a material designated as Ox-PE, exhibiting chemical reactivity. This modification could lead to an enhancement of compatibility between Ox-PE and other functionalized polymers. This approach has been exploited in this report to elaborate blends of Ox-PE with poly (ε-caprolactone) (PCL), a biodegradable polymer. Fourier Transform InfraRed spectroscopy (FTIR), Scanning Electron Microscopy (SEM) and thermal characterization by DSC, TGA were applied to investigate structural and thermal properties of PE/PCL (75/25 wt%/wt%) blends, compatibilized with 1 Phr and 5 Phr of Ethylene-co-Glycidyl MethAcrylate (EGMA) copolymer or with a Ox-PE/PCL mixture.Structural observations of the PE75/PCL25 blend by SEM revealed a phase separated morphology indicating incompatibility between PE and PCL. This was also confirmed by FTIR spectroscopy where no changes were noticed concerning the characteristic bands of either PE or PCL. Incorporating EGMA in the PE75/PCL25 blend resulted in reduced particle sizes of the dispersed PCL phase in the PE matrix confirming the reaction of epoxy groups of EGMA with hydroxyl end-groups of PCL at the interface. Regarding the thermal behavior, all PE/PCL blends exhibited an intermediate response between that of PE and PCL homopolymers. Interestingly, a high degree of compatibility was achieved for the Ox-PE75/PCL25 blend, together with a lower thermal stability compared to PE75/PCL25.