Coal dust can adsorb and retain volatile organic compounds (VOCs). This publication presents the identification and assessment of VOCs released from dust from hard coal preparation plants. An original method combining the microchamber technique µ-CTE with thermal desorption and gas chromatography (TD-GC-MS) was employed. Identification of compounds was based on comparison of mass spectra with the NIST library and with to the CRM EPA VOC Mixture 2 (Target Compounds) standard, which allowed for confident identification of individual VOCs. Qualitative and quantitative analyses revealed a broad range of VOCs, including alkanes, carcinogenic benzene, and 2-ethyl-1-hexanol, a component of flotation reagents. Experiments were conducted using five variants differing in thermal extraction temperature and duration to assess the kinetics of VOC release. At 22 °C, the analytes were below the limit of quantification (LOQ), whereas at 65 °C and 90 °C emission activation occurred, and extending extraction time to 60 minutes increased the amount of released compounds up to threefold. The results confirm the applicability of the µ-CTE method to evaluate the emission potential of coal dust and worker exposure risks, emphasizing the importance of selecting appropriate thermal extraction parameters for reliable and reproducible emission assessment.