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 °C in He atmosphere; 3) the similar ligands were also released from the burning cigarette containing respective complex.