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Herein, we report a review of our recent results on intermediate radiolytic products of dicyclohexanosubstituted crown ethers and some of crown-based systems, which were irradiated at 77K. Paramagnetic intermediate products were studied by ESR spectroscopy. Dicyclohexano-18-crown-6 (DCH18C6), di-tert-butylcyclohexano-18-crown-6 (DtBuCH18C6), their aqueous and 1-octanol solutions as well as complexes of DCH18C6 with nitrates and chlorides of alkali earth metals were chosen as the objects of investigation.