A new method for the detection of trace levels of organomercury species has been developed by combining the high enrichment capacity of purge and trap with aqueous phenylation derivatization. Phenylation products of monomethylmercury (MeHg) and monoethylmercury (EtHg) were first separated by capillary gas chromatography and then detected by atomic fluorescence spectrometry (AFS) or inductively coupled plasma mass spectrometry (ICPMS). This combination made it possible to simultaneously quantify trace or ultratrace level of MeHg and EtHg in environmental samples. Method detection limits were 0.03 ng/L for both MeHg and EtHg when AFS was used as the detector and 0.02 and 0.01 ng/L for MeHg and EtHg with ICPMS, respectively. Certified reference materials, IAEA-405 and DORM-2, were analyzed and the results were in accordance with certified values. Both MeHg and EtHg were detected in sediment samples collected from the Florida Everglades and a Canadian wetland. This new method has been validated for the direct detection of trace organomercury species in freshwater samples and has the additional benefits of being free from interference by Cl (-) and dissolved organic matter.