The aim of the research was to obtain intelligent and eco-friendly packaging materials by incorporating innovative additives of plant origin. For this purpose, natural substances, including green tea extract (polyphenon 60) and caffeic acid, were added to two types of biodegradable thermoplastics (Ingeo™ Biopolymer PLA 4043D and Bioplast GS 2189). The main techniques used to assess the impact of phytocompounds on materials’ thermal properties were differential scanning calorimetry (DSC) and thermogravimetry (TGA), which confirmed the improved resistance to thermo-oxidation. Moreover, in order to assess the activity of applied antioxidants, the samples were aged using a UV aging chamber and a weathering device, then retested in terms of dynamic mechanical properties (DMA), colour changing, Vicat softening temperature, and chemical structure, as studied using FT-IR spectra analysis. The results revealed that different types of aging did not cause significant differences in thermo-mechanical properties and chemical structure of the samples with natural antioxidants but induced colour changing. The obtained results indicate that polylactide (PLA) and Bioplast GS 2189, the plasticizer free thermoplastic biomaterial containing polylactide and starch (referred to as sPLA in the present article), both with added caffeic acid and green tea extract, can be applied as smart and eco-friendly packaging materials. The composites reveal better thermo-oxidative stability with reference to pure materials and are able to change colour as a result of the oxidation process, especially after UV exposure, providing information about the degree of material degradation.