Optimization and validation of headspace solid-phase microextraction method coupled with gas chromatography–triple quadrupole tandem mass spectrometry for simultaneous determination of volatile and semi-volatile organic compounds in coking wastewater treatment plant Abstract Industrial wastewater could be an important source for the emission of volatile (VOCs) and semi-volatile organic compounds (SVOCs), but little is known about it. In this study, a method for the identification and quantitation of 43 VOCs and SVOCs in coking wastewater was developed using a solvent-free equilibrium extraction method on the basis of headspace solid-phase microextraction accompanied by gas chromatography–triple quadrupole tandem mass spectrometry (HS-SPME-GC-MS/MS). To ensure good extraction efficiency, the parameters that have an effect on the HS-SPME-GC-MS/MS process were carefully optimized, in terms of fiber exposure time and temperature, pH, salt additives, sample volume, and desorption time. The HS-SPME method showed good linearity range with coefficients of determination (R2) ≥ 0.991 and achieving a satisfactory recoveries value (70–120%) with good relative standard deviations (RSDs) < 20% (precision). Furthermore, the purposed approach proved to be sensitive with low detection limits, where the values ranged from 0.03 to 3.01 μg/L. The real sample analysis result showed that 43 of VOCs and SVOCs were detected in raw coking wastewater, with 3-cresol as the dominant ones. Further, the method revealed that seven phenols, 11 polycyclic aromatic hydrocarbons, and five BTEX were detected even in the treated effluent. In conclusion, the HS-SPME method developed in this study is simple in sample preparation, convenient, sensitive, and could satisfy the requirement of the analysis of VOCs and SVOCs in coking wastewater.