A AgSCF3-mediated radical cascade cyclization/trifluoromethylthiolation of 1,6-enynes triggered by a C鈥揅 triple bond is developed. This protocol also provides another opportunity to construct a valuable trifluoromethylthio-substituted polycyclic fluorene system through the formations of one C鈥揝CF3 bond and two C鈥揅 bonds in a single step.