The syntheses and reactions of various thieno[2,3‐c]‐ and thieno[3,2‐c] pyridines are described. Molecular orbital calculations were performed on thieno[2,3‐c]pyridine (1) in order to determine the most susceptible sites to electrophilic and nucleophilic attack. Superdelocalizability values, Sr‐ are reported for each position in this molecule to give relative orders of reactivity towards the two types of reactions. Electrophilic attack was found to occur experimentally at C‐3 in all the thienopyridines studied. Peracid oxidation of thieno[2,3‐c]‐ and thieno[3,2‐c]pyridines produced only the N‐oxide. The lack of reactivity of certain thienopyridines under Vilsmeier formylation and Friedel‐Crafts acetylation conditions was related to their basicities. The dissociation constants of various thienopyridinium salts are reported.