Water-soluble metals exert a significant influence on human and ecosystem health. In this study, a comprehensive investigation was undertaken to elucidate the solubilities of metals in PM2.5 and potential influencing factors during the dry season of 2019–2020 in urban Guangzhou, South China. The observed average solubility was <20 % for Al, Fe, Sn, and Ti; 20–40 % for V, Cr, Sb, Pb, and Ni; 40–60 % for Ba and Cu; and 60–80 % for Zn, As, Se, Cd, and Mn. Metals (Al, Ti, and Fe) originated from crustal sources (e.g., soil dust) have much lower solubilities than those (Mn, Zn, As, Se, Cd, and Ba) from fossil fuel combustion sources (e.g., traffic emission, coal combustion), suggesting the dominant role the metal sources played on solubility. Enhanced solubilities of Cu, As, Se, Cd, Sn, Sb, and Pb were associated with aerosol acidity, while those of V, Cr, Mn, Ni, Zn, and Ba were linked to organic acid complexation. For the three crustal metals, the solubilities of Al and Ti primarily depended on aerosol acidity, whereas the solubility of Fe depended on both aerosol acidity under pH < 2 conditions and organic acid complexation under pH > 2 conditions. These findings underscore the primary influence of inherent properties of the metals on their solubility and reveal the varying impacts of atmospheric physicochemical processes, with changes in their solubilities being <10 % for Cd, Sn, Sb, and Pb, 10–20 % for Cu, Cr, Mn, Ni, and Ba, and 20–30 % for As, Se, and Zn. Display omitted •Crustal metals are less soluble than those from combustion.•Cu, As, Se, Cd, Sn, Sb, Pb, Al, and Ti solubilities increase with aerosol acidity.•V, Cr, Mn, Ni, Zn, and Ba solubilities rise due to organic acid complexation.•Fe solubility depends on aerosol acidity and organic acid complexation.