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Dissolved organic sulfur (DOS) is an important component of dissolved organic matter (DOM) and widely exists at the land‐atmosphere interface. However, the characterization of DOS at the molecular level among different environmental samples in coastal regions has not been sufficiently focused. Here, we investigated DOS in aerosol, rainwater, and river water samples in Shanghai using an improved method–online liquid chromatography coupled to Fourier transform ion cyclotron resonance mass spectrometry (LC‐FT‐ICR MS). This system is utilized to separate DOS from complicated environmental matrices. The results showed that the average relative abundance of DOS in three different environmental media (aerosol, rainwater, and river water samples) accounted for 16.8%, 21.9% and 13.1%, respectively. The common molecules of the three mediums in coastal Shanghai contain an abundance of aromatic and aliphatic DOS of anthropogenic origin in addition to the natural sources of sea spray. Notably, results from a new structural classification scheme for DOS demonstrate that anthropogenic sulfonates and their derivatives are widely spread, although their molecular diversity in different medium was recorded due to complex environmental conditions and diverse sources. Plain Language Summary: Ion suppression of abundant non‐sulfur containing species hinders the detection of dissolved organic sulfur species by direct infusion electrospray ionization mass spectrometry. A newly developed method is proposed to evaluate organic sulfur‐containing compounds at the molecular level using an online liquid chromatography coupled to ultrahigh resolution mass spectrometry, which was applied to aerosol, rainwater, and river water samples in Shanghai. Our study suggests that the novel method allows a detailed investigation of organic sulfur‐containing compounds and provides molecular evidence of the ubiquitous presence of anthropogenic DOS in the ambient environment. Key Points: The ubiquity of natural and anthropogenic dissolved organic sulfur was observed at the water‐atmosphere interfaceNatural dissolved organic sulfur at the coastal water‐atmosphere interface is mainly from sea spray‐based biological sourcesOnline liquid chromatography coupled to FT‐ICR Mass Spectrometry is an ideal system to separate dissolved organic sulfur [ABSTRACT FROM AUTHOR]

• Rainwater DOM along the yangtze river were characterized by optical properties and FT-ICR MS. • Natural and anthropogenic emissions and climatic conditions shaped the chemodiversity of rainwater DOM. • Biogenic secondary organic compounds widely contributed to rainwater DOM along the Yangtze River Basin. Rainwater dissolved organic matter (DOM) plays an important role in the biogeochemical cycle and evolution of organic matter in the land-atmosphere interface. To better understand their sources and molecular composition in the atmosphere, rainwater samples were collected at six different locations along the Yangtze River Basin. Based on the application of a combined approach including excitation-emission matrix (EEM) fluorescence and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), various sources (terrestrial, anthropogenic, and autochthonous sources) of rainwater DOM were revealed. Results show that the derivatives of biogenic volatile organic compounds were widely distributed and contributed to rainwater DOM along the Yangtze River Basin. In the up-river city Batang, rainwater DOM was affected by the long-range atmospheric transport due to the Indian summer monsoon. Lijiang, a city on the southeastern edge of Tibetan plateau, was related to strong local biomass burning. The industrial cities of Panzhihua and Luzhou showed large differences in organic composition due to distinct industrial types. Fuling, a district in Chongqing Municipality, was significantly contributed by aged organics from biomass burning. While rainwater DOM in Shanghai, a coastal megacity, contained a high fraction of sea spray organics. Further, more than 70% of rainwater DOM molecules are associated with 36 typical transformation mechanisms during rainwater-scavenging processes, e.g., oxidation reactions, dealkylation and decarboxylation. Our study demonstrates that local natural and anthropogenic emissions and climatic conditions strongly shaped the chemodiversity and possible precursor-product pairs of rainwater DOM along the Yangtze River Basin, which helps to better understand the biogeochemical cycles of organic matter in a large-scale watershed under the influence of human activities. [Display omitted] [ABSTRACT FROM AUTHOR]