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Dibromoderivatives of benzofused chalcogen-nitrogen heterocycles are important precursors in the synthesis of various photovoltaic materials. 4,7-Dibromobenzo[<i>d</i>][1,2,3]thiadiazole is a practically unexplored compound in this series. In this communication, it was shown that the nucleophilic substitution of 4,7-dibromobenzo[<i>d</i>][1,2,3]thiadiazole with morpholine gave selectively 4-substituted product—4-(7-bromobenzo[<i>d</i>][1,2,3]thiadiazol-4-yl)morpholine. The structure of the newly synthesized compound was established by means of elemental analysis, high resolution mass-spectrometry, ¹H, ¹³C NMR, and IR spectroscopy, mass-spectrometry, and X-ray analysis.