The molecular composition of organic aerosols in ambient PM 2.5 was investigated in an urban area in the Guanzhong basin of northwest China during a severe regional haze episode in the winter of 2018/2019. Organic matter, accounting for 20−35% of PM 2.5 mass concentration, was characterized using direct infusion and electrospray ionization coupled with high-resolution Orbitrap mass spectrometry. The number of organic molecular formula assignments was primarily dominated by organosulfur species (OrgS, including CHOS and CHONS) in negative ion mode. The number and peak signal intensity of OrgS distinctly increased during the severe haze episode. Organosulfates and nitrooxyorganosulfates constituted the majority number (72−94%) of OrgS over the entire period. Although the OrgS were mostly present in aliphatic molecular structures, an increase in the number of polycyclic aromatic OrgS on haze days revealed the enhanced contribution from anthropogenic sources. The number of OrgS strongly correlated with ambient relative humidity and the oxidation ratios of sulfur and nitrogen, suggesting the important roles of aqueous phase chemistry and atmospheric oxidation in the formation of OrgS. A thorough understanding of the significance of OrgS will be essential to assess and mitigate the adverse impacts of haze pollution.