Divergent　synthesis　for　precise　constructions　of　cyclic　unsymmetrical　diaryl　disulfides　or　diselenides　and　polythiophenes　from　CF3-containing　1,3-enynes　and　S8　was　developed　when　the　ortho　group　is　F,　Cl,　Br,　and　NO2　on　aromatic　rings.　Meanwhile,　disulfides　(diselenides)　were　also　quickly　constructed　when　the　ortho　group　is　H.　These　transformations　undergo　cascade　thiophene　construction/selective　C3-position　thiolation　process,　featuring　simple　operations,　divergent　synthesis,　broad　substrate　scope,　readily　available　starting　materials,　and　valuable　products.　A　novel　plausible　radical　annulation　process　was　proposed　and　validated　by　DFT　calculations　for　the　first　time.　A　series　of　derivatizations　about　the　thiophene　(TBT)　and　disulfides　were　also　well-represented.　©　2020　Wiley-VCH　GmbH