Triptycene-derived vinyl sulfide polymers 4a-d were synthesized from a versatile catalyst-free thiol-yne click reaction using 1,4-diethynyl triptycene 1 with various aryl dithiol building blocks 3a-d. The resulting triptycene-bearing poly(vinylene sulfide)s 4a-d display excellent solubility and chemical stability allowing for their structural, thermal, and photophysical characterization by various instrumental analysis techniques. The thioether groups in polymers 4a-d were selectively oxidized into their respective sulfone derivatives via mild reaction conditions affording the corresponding triptycene-based poly(vinylene sulfone)s 5a-d in quantitative yield.