A series of 3-(hetero)aryl-substituted benzo[b]thieno[2,3-d]thiophenes, bearing various electron withdrawing groups at C-2 position of their scaffolds, were obtained using a convenient approach based on the Fiesselmann thiophene synthesis. To realize this strategy, the Friedel-Crafts acylation of (hetero)arenes with easily accessible 3-chlorobenzo[b]thiophene-2-carbonyl chlorides was initially performed to afford 3-chloro-2-(hetero)aroylbenzo[b]thiophenes. The latter ketones were treated either with methyl thioglycolate in the presence of DBU and calcium oxide powder or successively with sodium sulfide, an alkylating agent, containing methylene active component, and also DBU and calcium oxide, to form the desired benzo[b]thieno[2,3-d]thiophene derivatives. In addition, similar benzo[4,5]selenopheno[3,2-b]thiophene derivatives were prepared in the same manner using 3-bromobenzo[b]selenophen-2-yl substrates. The obtained functional derivatives of both benzo[b]thieno[2,3-d]thiophene and benzo[4,5]selenopheno[3,2-b]thiophene are of interest for further elaboration of organic semiconductor materials.