The viability of producing environment-friendly blends of HDPE and LDPE with a commercial biodegradable masterbatch containing starch and polyethylene was studied. The service life of these blends was simulated by means of a thermo-oxidative treatment, and their further disposal in landfill was modeled using an accelerated soil burial test. Characterization was carried out in terms of their calorimetric and thermogravimetric properties. Thermo-oxidative treatment causes an increase in the crystalline content of both components of the blends, and promotes a segregation of the crystallite sizes of polyethylene. The soil burial test leads to changes in the crystalline content of the biodegradable material, which is influenced by the polyolefinic matrix used. The kinetics of the thermal decomposition of these blends was studied using the Hirata and the Broido models. Thermogravimetric results reveal that the thermo-oxidative treatment causes a decrease in the activation energy of the thermal decomposition process of both components in the blends, regardless of the type of polyethylene used. The thermooxidative treatment mainly modifies the thermal properties of starch during the degradation process in soil, especially in the LDPE blends. Synergetic degradation of these blends is a complex process that is dependent on the polyolefinic matrix used and mainly causes morphological changes.