Metals are released in effluents of most of combustion processes and are under intensive regulations. To improve our knowledge of combustion process and their resulting emission of metal to the atmosphere, we have developed an approach allowing usto distinguish between gaseous and particulate state of the elements emitted. This study was conducted on the emission of volatile metallic species emitted from a coal combustion plant where low/medium volatile coal (high-grade ash) was burnt. The occurrence of volatile metal species emission was investigated by cryofocusing sampling procedure and detection using low-temperature packed-column gas chromatography coupled with inductively coupled plasma-mass spectrometry as multielement detector (LT-GC/ICP-MS). Samples were collected in the stack through the routine heated sampling line of the plant downstream from the electrostatic precipitator. The gaseous samples were trapped with a cryogenic device and analyzed by LT-GC/ICP-MS. During the combustion process, seven volatile metal species were detected: three for Se, one for Sn, two for Hg, and one for Cu. Thermodynamic calculations and experimental metal species spiking experiments suggest that the following volatile metal species are present in the flue gas during the combustion process: COSe, CSSe, CSe2, SeCl2, Hg0, HgCl2, CuO-CuSO4 or CuSO4 x H2O, and SnO2 or SnCl2. The quantification of volatile species was compared to results traditionally obtained by standardized impinger-based sampling and analysis techniques recommended for flue gas combustion characterization. Results showed that concentrations obtained with the standard impinger approach are at least 10 times higher than obtained with cryogenic sampling, suggesting the trapping microaerosols in the traditional methods. Total metal concentrations in particles are also reported and discussed.