A simple and reliable technique has been developed and used to detect odorous gases, i.e. propionic and butyric acids, carbon disulfide, dimethyl sulfide, dimethyl disulfide, and trimethylamine, emitted from various materials generated by the wastewater treatment process. The method detection limits are in the low ppb range and comparable to the odor threshold for human detection. In this study solid phase microextraction (SPME) was employed to characterize and quantify odorous compounds in the headspace over samples collected from various unit processes at the District of Columbia Wastewater Treatment Plant, Washington DC, USA. The patterns of odorous chemicals released from wastewater influent, thickened sludge, dewatered sludge and biosolids were evaluated. Volatile reduced sulfurs were more prevalent in samples collected from downstream processes and corresponded with decreased oxidation-reduction potential (ORP) conditions. Volatile fatty acids were consistently identified in the primary gravity thickeners, while trimethylamine could only be detected from biosolids after the post-liming process.