Abstract: In order to investigate their pyrolytic behavior,four complexes of maltol/ethyl maltol and zinc (Ⅱ)/calcium(Ⅱ)were prepared and characterized by ¹H NMR,¹³C NMR,UV,IR spectra. The pyrolytic experiments of the complex alone or in cigarettes were conducted by on-line CDS5200 pyrolyser-GC/MS. The results showed that: 1)the complexation between maltol/ethyl maltol and zinc(Ⅱ)/calcium(Ⅱ)occurred obviously; 2) relevant maltol or ethyl maltol ligands released effectively from each pyrolyzed complex at 400℃ in He atmosphere;3)the similar ligands were also released from the burning cigarette containing respective complex.