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<p>Reactive organic gases (ROGs), as important precursors of secondary pollutants, are not well resolved as their chemical complexity has challenged their quantification in many studies. Here, a near-complete speciation of ROG emissions from residential combustion was developed by the combination of proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS) with a gas chromatography system equipped with a mass spectrometer and a flame ionization detector (GC-MS/FID), including 1049 species in all. Among them, 125 identified species, <span class="inline-formula">∼</span> 90 % of the total ROG masses, were applied to evaluate their emission characteristics through real combustion samplings in rural households of China. The study revealed that with 55 species, mainly oxygenated species, higher hydrocarbons with <span class="inline-formula">≥</span>8 carbon atoms, and nitrogen-containing species, previously un- and under-characterized, ROG emissions from residential coal and biomass combustion were underestimated by 44.3 % <span class="inline-formula">±</span> 11.8 % and 22.7 % <span class="inline-formula">±</span> 3.9 %, respectively, which further amplified the underestimation of secondary organic aerosol formation potential (SOAP) as high as 70.3 % <span class="inline-formula">±</span> 1.6 % and 89.2 % <span class="inline-formula">±</span> 1.0 %, respectively. The hydroxyl radical reactivity (OHR) of ROG emissions was also undervalued significantly. The study provided a feasible method for the near-complete speciation of ROGs in the atmosphere and highlighted the importance of acquiring completely speciated measurement of ROGs from residential emissions, as well as other processes.</p>