Affinity polymeric adsorbents useful for the separation of compounds which are derivatives of phenols, heterocycles and other compounds containing two polar moieties were prepared by a covalent imprinting approach. Such separation, for example, would facilitate the analytical detection and quantification of each individual compound especially when present in complex sample matrix. The synthetic method, utilised for the preparation of the polymers, is based on co-polymerization of diacrylate esters of hydroxyphenols (catechol, resorcinol and hydroquinone) with an appropriate cross-linker followed by alkaline hydrolysis of the esters and release of the corresponding phenol. The resulting swellable materials contain cavities with adjustable size and orientation of two carboxylic groups suited for the binding of molecules with appropriate size and complementary orientation of polar groups. In contrast to conventional MIPs the synthesized polymers have selectivity not only for the phenolic templates, but also for a group of compounds with suitable orientations of polar functionalities, such as aromatic nitrogen, amino or hydroxyl groups. Polymers demonstrated different affinity to ortho-, meta- and para-isomers of hydroxyphenols, hydroxypyridines and diazine heterocycles.