We explored chemical strategies to promote intermolecular cross-linking induced by fluorinated alkyl units under ionizing radiation. To this end, we synthesized a compound containing two fluoroalkyl moieties and two vinylsilyl groups, which exhibited more efficient cross-linking under accelerated electron-beam irradiation compared to vinyl-lacking analogues. Under extreme ultraviolet irradiation, the vinylsilyl-containing compound was similarly converted into a cross-linked, insoluble material, enabling the formation of sub-20 nm structures.