Novel tetrafluoro-λ⁶-sulfanyl-containing oligomers prepared by visible light-promoted addition of 1,4-(bis-chlorotetrafluoro-λ⁶-sulfanyl) benzene or 1,3-(bis-chlorotetrafluoro-λ⁶-sulfanyl) benzene to either 1,4-diethynyl benzene or the 1,3-diethynyl isomers form hard, stress resistant thin films on spin casting. The isomeric oligomers were utilized to establish a structure-function relationship for the mechanical properties of films prepared from the oligomers. The Young’s moduli of 145-nm-thick cured films could reach 60 GPa. The measured hardnesses, between 1.57 and 2.77 GPa, were more than double those of polymethyl methacrylate (PMMA) films. Curing of the tetrafluoro-λ⁶-sulfanyl-containing polymer films by UV irradiation resulted in coatings that exhibited remarkable hardness and modulus with good surface adhesion to silicon.