The chemical performance of 5‐bromo‐2‐(bromoacetyl)‐thiophene (1) was tested toward the reaction with numerous bi‐nucleophilic reagents (namely; 2‐aminobenzothiazoles, 2‐aminothiazole, 2‐aminotetrazole, 2‐aminotriazole, 2‐aminopyridines, 2‐aminobenzimidazole and o‐phenylenediamine). Therefore, a series of bridged nitrogen heterocycles bearing thiophene moiety 3, 5, 7, 9, 11, 13 and 15, respectively was synthesized. In addition, the reaction of 5‐bromo‐2‐(bromoacetyl)‐thiophene with the thiocarbamoyl compounds 17, 19 and/or 24 afforded the corresponding thienyl‐thiazoles 18 or dithien‐2‐yl ketones 20 and 25, based on the reaction conditions. Treatment of 1 with 2‐mercapto‐4,6‐dimethylnicotinonitrile was achieved to obtain the target dithien‐2‐yl ketone 28. The new synthesized scaffolds were examined for their antioxidant activity by means of ABTS antioxidant assay. The thienyl‐thiazole scaffold 18c and 2‐((2‐[thiophen‐2‐yl]‐2‐oxoethyl)thio)nicotinonitrile derivative 27 displayed a reasonable radical scavenging activity.