A rationally designed polymer (RDP) capable of recognizing α-tocopherol and other minor components in sunflower oil has been produced. It is known that sunflower oil is a source of various physiologically active compounds. Unfortunately, they are present in very minor quantities which make their purification from the complex oil matrix problematic. An extraction method presented here was developed with particular attention to the selectivity, efficiency and precision of the extraction process. The methacrylic acid-based RDP in combination with the optimised purification method allowed the extraction of α-tocopherol with 94% recovery. The synthesised polymer was used successfully to extract α-tocopherol together with other essential minor components of sunflower oil without any pre-treatment step. According to GC/MS, the compounds ‘harvested’ from sunflower oil using the developed polymer included palmitic, oleic and linoleic acids, α-tocopherol, campesterol, stigmasterol, and β-sitosterol