Thieno[3,2‐b]pyrroles with N‐arylamino and 3‐thienoylpropyl functionalities are synthesized in up to 68 % yield from acylthiophenes, acetylene gas and hydrazines via the intermediate methylene‐6,8‐dioxabicyclo[3.2.1]octanes, which undergo multi‐position structural reorganization into the title compounds in the presence of hydrazines and TFA.