AbstractSimple and convenient methods for the synthesis of a range of new 1,2,3‐thiadiazole derivatives, including ethyl esters, alcohols, and aldehydes, were developed. Moreover, twenty‐nine new structurally diverse 4‐vinyl‐1,2,3‐thiadiazoles were successfully synthesized in 18–89 % yield via Knoevenagel condensation. NOESY‐experiments were performed for E/Z‐assignment of isomeric mixtures. The structure of five of the new vinylic derivatives has been confirmed using X‐ray diffraction analysis. Using the example of ethyl (E)‐2‐cyano‐3‐(5‐(pyrrolidin‐1‐yl)‐1,2,3‐thiadiazol‐4‐yl)acrylate, the possibility of dimerization with the formation of diethyl(1R,2R,3S,4S)‐1,3‐dicyano‐2,4‐bis(5‐(pyrrolidin‐1‐yl)‐1,2,3‐thiadiazol‐4‐yl)cyclobutane‐1,3‐dicarboxylate was demonstrated, allowing the first 1,2,3‐thiadiazole substituted cyclobutane to be synthesized.