Thiazole rings have been often encountered in the structure of antibiotic or antitumor drugs. An easy synthesis of them has revealed itself necessary in order to elucidate the mechanism of action of these naturally occurring substances. A method of preparation of conjugated b‐ethylenic thiazole[3,2‐b] [1,2,4]triazoles by heating a 3‐thio substituted [1,2,4]triazole in the presence of polyphosphoric acid is reported here, giving the expected product in a 60% yield.