Abstract Starting from the readily available aryl 2‐substituted‐4‐methyl‐5‐thiazolyl ketones, a series of 2,6‐disubstituted‐thieno[3,4‐d]thiazoles and 2,6‐disubstituted‐selenolo[3,4‐d]thiazoles were prepared. The structures of these compounds were confirmed by analytical, spectroscopic methods and through the reaction with dimethyl acetylenedicarboxylate.