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The convenient and multigram synthesis of a linear benzo[<i>b</i>]dithiophene (BDT) structure is proposed (dimethyl 3,7-diamino-4,8-bis((2-methoxy-2-oxoethyl)thio)benzo[1,2-<i>b</i>:4,5-<i>b’</i>]dithiophene-2,6-dicarboxylate). The starting materials are commercially available 2,3,5,6-tetrachloroterephthalonitrile and methyl 2-mercaptoacetate, which undergo aromatic substitution, followed by a cyclization reaction in basic conditions to form suitable BDT for potential optoelectronic applications.