TSP and 9-stage size-segregated samples were simultaneously collected in Xi'an during the spring of 2013 and analyzed for organic aerosols (OA) on a molecular level. n-Alkanes were the dominant compound class during the whole campaign, followed by fatty acids. High molecular weight (HMW) n-alkanes and fatty acids dominated in the coarse mode particles (>1.1 μm) during the dust event, indicating they were mostly originated from surface soil and plants in the upwind regions. Low-volatile anthropogenic compounds such as benzo(e)pyrene (BeP) and bisphenol A (BPA) dominated in the fine mode particles during the whole campaign. In contrast, semi-volatile anthropogenic compounds such as phenanthrene (Phe) and di-n-butyl phthalates (DBP) showed a bimodal size distribution with a significant increase in the coarse mode during the dust event due to their vaporization from the fine mode particles and the subsequent adsorption on the dust surface. Secondary organic aerosols (SOA) in Xi'an during the dust storm period were predominantly enriched on the coarse particles, which can be ascribed to the adsorption and subsequent oxidation of gas-phase hydrophilic organics on the aqueous-phase of hygroscopic dust surface (e.g., mirabilite). Our work suggested an important role of multiphase reaction in evolution of aerosol chemistry during the dust long-range transport process. •n-Alkanes were the dominant organic compound class during the whole campaign.•Low-volatile anthropogenic compounds dominated in the fine mode particles.•SOA were predominantly enriched on the coarse particles during the dust storm.•Multiphase reaction has an important role in evolution of aerosol chemistry.