Various water-soluble inorganic compounds, including Na+, NH4+, K+, Ca2+, Mg2+, Cl-, NO3-, PO43- and SO42- were analyzed in 130 sets of size-segregated (< 0.49, 0.49–0.95, 0.95–1.5, 1.5–3.0, 3.0–7.2, 7.2–10.0 μm) aerosol samples, collected from March 2013 to April 2014 in Guangzhou, China. SO42- was unimodally distributed and peaked at a typical droplet mode (0.49–0.95 μm). However, the distribution of NO3- significantly varied over the four seasons. It was unimodally distributed in summer and autumn, with the peak at a coarse mode (3.0–10 μm), and bimodally distributed in winter and spring, with peaks at 0.49–0.95 μm and 3.0–10 μm, respectively. The coarse-mode NO3- was mainly related to the influence of soil/dust. The additional mode during winter and spring was attributed to the formation of ammonium nitrate. Compared with clean days, polluted days favored the formation of SO42- in summer and autumn, and NO3- in winter and spring. The sulfur oxidation ratios (SOR) for < 0.49, 0.49–0.95 and 0.95–1.5 μm particles were negatively correlated with relative humidity (RH) in spring, summer and autumn, respectively. However, SOR for 0.49–3.0 μm particles was positively correlated with RH in winter, implying an important contribution from the aqueous oxidation of SO2. Further analysis shows that SO42- in < 0.49 μm particles was mainly formed through gas-phase photochemical oxidation of SO2 over the four seasons. The formation of NO3- was mainly attributed to heterogeneous reactions at 1.5–3.0 μm particles over the four seasons and homogeneous gas-phase reactions at < 0.49 μm particles in winter. Correlation analysis further shows a positive influence of biomass burning in the formation of nitrate and sulfate. The average pH of PM3 was calculated to be 2.6–5.6. Thus, the aqueous oxidation of SO2 by NO2 plays a limited role in the formation of sulfate in the atmosphere of Guangzhou.