Over 120 polyaromatic hydrocarbons (PAHs) have been identified in urban pollution, of which 16 have been specified by the United States Environmental Protection Agency (EPA) as priority pollutants. Increased urban concentrations from anthropogenic sources are of particular concern because many of them show carcinogenic and/or mutagenic properties. In this study thermal extraction (TE) coupled with GC/TOF-MS and solvent extraction coupled with GC/MS were utilized to determine the PAH concentrations in fly ash samples collected from a bench-scale 0.1 MWth fluidized bed combustor (FBC). In addition to the evaluation of the analysis procedures including conventional solvent extraction and thermal extraction, a comprehensive study of the effect of operating conditions on PAH emissions in fly ashes samples was conducted. The experimental results indicate the majority of PAHs (two and three fused-ring systems) found in the solid phase (fly ash) are derived from breakdown reactions during the combustion and/or pyrolysis processes in an FBC system. The results for PAH analysis obtained with the TE/GC/TOF-MS technique were comparable to or better than the conventional solvent extraction-GC/MS technique.