The rapid and solvent-free determination of organophosphate esters (OPEs) in aqueous samples via one-step microwave-assisted headspace solid-phase microextraction (MA-HS-SPME) followed by gas chromatography-mass spectrometry (GC-MS) analysis is described. Tri-n-butyl phosphate (TnBP) and tris-(2-ethylhexyl) phosphate (TEHP) were selected as model compounds for the method of development and validation. The effects of various extraction parameters for the quantitative extraction of these analytes by MA-HS-SPME were systematically investigated and optimized. The analytes, in a 20 mL water sample (in a 40 mL sample bottle containing 2 g of NaCl, pH 3.0), were efficiently extracted by a polydimethylsiloxane-divinylbenzene (PDMS-DVB) fiber placed in the headspace when the system was microwave irradiated at 140W for 5 min. The limits of quantification (LOQs) for TnBP and TEHP were 0.5 and 4 ng/L, respectively. Using the standard addition method, MA-HS-SPME coupled with GC-MS was utilized to determine selected OPEs in surface water and wastewater treatment plants (WWTP) influent/effluent samples. Preliminary results show that TnBP was commonly detected OPEs in these aqueous samples, the correlation coefficients (r(2)) of the standard addition curves were greater than 0.9822, indicating that the developed method appears to be a good alternative technique for analyzing OPEs in aqueous samples. (C) 2011 Elsevier B.V. All rights reserved.