The Guanzhong basin is a part of the three top priority regions in China's blue sky action as of 2019. Understanding the chemical composition, sources, and atmospheric process of aerosol in this region is therefore imperative for improving air quality. In this study, we present, for the first time, the seasonal variations of organic aerosol (OA) in Xi'an, the largest city in the Guanzhong basin. Biomass burning OA (BBOA) and oxidized OA (OOA) contributed >50% of OA in both autumn and winter. The average concentrations of BBOA in autumn (14.8 ± 5.1 μg m) and winter (11.6 ± 6.8 μg m) were similar. The fractional contribution of BBOA to total OA, however, decreased from 31.9% in autumn to 15.3% in winter, because of enhanced contributions from other sources in winter. The OOA fraction in OA increased largely from 20.9% in autumn to 34.9% in winter, likely due to enhanced emissions of precursors and stagnant meteorological conditions which facilitate the accumulation and secondary formation. A large increase in OOA concentration was observed during polluted days, by a factor of ~4 in autumn and ~6 in winter compared to clean days. In both seasons, OOA formation was most likely dominated by photochemical oxidation when aerosol liquid water content was <30 μg m or by aqueous-phase processes when O was <35 ppb. A higher concentration of BBOA was observed for air masses circulated within the Guanzhong basin (16.5–18.1 μg m), compared to air masses from Northwest and West (10.9–14.5 μg m). Furthermore, compared with OA fraction in non-refractory PM in other regions of China, BBOA (17–19%) and coal combustion OA (10–20%) were major emission sources in the Guanzhong Basin and the BTH region, respectively, whereas OOA (10–34%) was an important source in all studied regions.