In this study, a number of 3-aryl-substituted benzo[b]selenopheno[2,3-d]thiophene derivatives containing electron-withdrawing groups (EWG), such as cyano, carbomethoxy or benzoyl, at C-2 position were readily obtained using one-pot procedure from 2-aroyl-3-chlorobenzo[b]thiophenes. To realize this protocol, the starting substrates were treated sequentially with sodium selenide and triethylammonium bromide, an alkylating agent with methylene-active part, and then potassium carbonate, thus affording the desired compounds. In addition, 2-cyano- and 2- carbomethoxy-substituted 3-hydroxybenzo[b]selenopheno[2,3-d]thiophenes were synthesized from methyl 3-chlorobenzo[b]thiophene-2-carboxylate using the same approach, except that the intermediate benzo[b]thiophene-2-carboxylates, bearing - SeCH2CN and -SeCH2CO2Me parts at C-3 position, were isolated and then cyclized using sodium methoxide instead of potassium carbonate. (C) 2022 Elsevier Ltd. All rights reserved.