Polymers made of renewable raw materials are attracting increasing interest because of diminishing oil deposits and the pro-ecological character of such polymers. The aim of our study was to create composites of polycaprolactone (PLC) and epoxidised natural rubber (ENR) using innovative natural additives. The cross-linking of composites was performed with the use of amino acids, flavonoids and fatty acids to eliminate sulphur and peroxides that are not environmentally friendly. Some of the cross-linkers used fulfilled the role of antioxidants. Based on WAXD, SEM and DSC examinations, we found good miscibility and compatibility of the polymers. All the innovative compounds used appeared to be good cross-linkers. The best ENR/PCL composite cross-linking effect was obtained with the use of quercetin, a flavonoid that also appeared to be a good anti-ageing substance. The mechanical properties of the composites were satisfactory. Their tensile strength ranged from 10 to 22MPa at elongation in the range of 292–436%. The ENR/PCL composites were more thermally stable than ENR vulcanisates due to their improved resistance to oxidation. Undoubtedly, these composites exhibit the features of innovative pro-ecological products. They meet current ecological requirements and can be widely used in medicine as well as in materials for common use, such as food packaging.