Abstract The azolylmethyl p‐chlorobenzoates (V), synthesized from the (thio)amides (I) as outlined in the reaction scheme, are submitted to flash vacuum pyrolysis, forming the heterocyclic o‐xylylene‐like intermediates (VI) which are trapped in situ by co‐condensation with thiophenol (VII) or sulfur dioxide (XII) to yield the regioisomeric thiazoles (VIII) and (IX), the oxazoles (X) and (XI), or the sulfolene‐fused oxazole (XIII).