A highly efficient unprecedented catalyst-free microwave-assisted procedure for synthesizing benzo[d]imidazo[2,1-b]thiazoles and N-alkylated 2-aminobenzo[d]oxazol in green media was developed. The transformation provided rapid access to functionalized benzo[d]imidazo[2,1-b]thiazoles from 2-aminobenzothiazole and N-alkylated 2-aminobenzo[d]oxazole from 2-aminobenzoxazole scaffolds under mild transition-metal-free conditions. This synthetic manipulation is expected to greatly expand the repertoire of reaction types in heterocyclic chemistry and pave the way for new syntheses of bioactive compounds.