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Low temperature (77K) radiolysis of di-(tert-butylcyclohexano)-18-crown-6 and its solutions in 1-octanol was studied by ESR spectroscopy. Macrocyclic –CH2–ĊH–O– and acyclic –O=C(H)–ĊH– radicals were identified as the principal radical products in pure crown ether. Radiation-chemical yields of these radicals were approximately equal to each other. In addition to abovementioned radicals, alkyl type –CH2–ĊH–CH2– and hydroxyalkyl R–ĊH–OH radicals were detected in irradiated octanol solutions. In this case, acyclic radicals result only from direct radiolysis of crown ether. No radical product resulted from t-Bu and cyclohexyl moieties were observed in crown ether and its solutions.