The synthesis of 2,4‐diarylthiophenes via the reaction between substituted styrenes and sulfur is generally referred as Baumann‐Fromm thiophene synthesis. Besides the major product of 2,4‐diarylthiophene, some minor 2,5‐diarylthiophenes have also been reported in this reaction. Similarly, butadiynes can react with hydrogen sulfide to afford thiophenes. However, at 600°C in the presence of a ferrous sulfide‐alumina catalyst, styrene reacted with hydrogen sulfide to give 60% benzothiophene.