Abstract <p>Telomers with a chain length dependent on the monomer content in solution have been synthesized in tetrafluoroethylene solutions in propylene oxide with concentrations of 0.08–4.2 mol/L under exposure to gamma rays of a ⁶⁰Co source at room temperature. Monomer consumption during irradiation has been monitored calorimetrically and gravimetrically; the complete monomer conversion is observed at radiation doses of 10–15 kGy. The molecular mass characteristics of the radiolysis products have been determined by thermogravimetry. It has been found that telomers with a chain length of less than 6 units form true solutions; colloidal solutions and dense gels are formed at the degree of polymerization of the monomer of 6–15 and above 15, respectively. It has been revealed that the terminal functional epoxy group is preserved in the propylene oxide fluorotelomer structure. The morphology of the coating layers has been studied by atomic force microscopy.</p>