A fast and green approach for the non-chromatographic assaying of volatile metalorganic compounds (VMOCs) is presented, involving the use of thermal desorption microwave-induced plasma optical emission spectrometry for the multi-species simultaneous determination of VMOCs in wastewater plant samples after headspace solid-phase microextraction (HSSPME-TD-MIP-OES), and optimized as a tool for the assessment of ambient exposure to hazardous VMOC pollutants. With the aim of VMOC monitoring, all species are separated and quantified within 10 s in comparison with about 10–20 min required by conventional GC-based procedures. Calibration against aqueous standards was carried out for several metalorganic species. The method was successfully applied for the quantitative extraction of As, Bi, Hg, Sb, Si and Sn compounds. Limits of detection ranging from 5 to 30 ng L⁻¹ and relative standard deviations lower than 4% were obtained. The method is appropriate for high-sample-throughput measurements, and it proved to be suitable for the analysis of wastewater and sewage sludge samples.