Tobacco flavours, as important tobacco additives, have attracted extensive attention to their stability. The demand for the stability of tobacco flavours is growing especially with the popularity of novel tobacco products. Volatile flavour molecules can be coordinated with metal ions to prepare flavour metal complexes and to improve the thermal stability of flavours. In this study, four ethyl maltol-containing metal complexes were synthesised by the coordination between ethyl maltol and ions of Fe³⁺, Al³⁺, Zn²⁺ and Ca²⁺. The structures of those ethyl maltol-metal complexes were characterized by nuclear magnetic resonance (NMR) spectroscopy, single-crystal and powder X-ray diffractions and ultraviolet-visible (UV-Vis) spectrophotometry. The thermal behaviour and pyrolysis products were then investigated by thermogravimetry, single photoionisation mass spectrometry (SPIMS) and pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS). The NMR and other spectral results confirmed that four metal complexes were synthesised with proper and specific structures. The results of thermal analysis showed that the four metal complexes could release ethyl maltol at temperatures higher than the phase transition temperature of ethyl maltol, indicative of the good thermal stability of synthesised complexes. The differences among metal ions caused the temperature of maximum weight loss rate of each complex to change in the range of 270 °C - 350 °C. The peak temperatures of ethyl maltol released from Fe³⁺, Al³⁺, Zn²⁺ and Ca²⁺ metal complexes were 279 °C, 346 °C, 294 °C and 337 °C, respectively. The above results indicate that the exploitation of metal complexes as flavour precursors is a feasible strategy not only to enhance the thermal stability but also to regulate the release temperature of flavours.