The release behaviors of potentially toxic elements (PTEs) associated with water-dispersible colloids (WDCs) in contaminated soils are of considerable public concern. However, little information is available on the size distribution and elemental composition of WDCs and their effects on the release of PTEs in contaminated soils under long-term acid rain. Here, a quantitative accelerated aging leaching test was conducted to evaluate the long-term release risks of PTEs from four contaminated agricultural soil types exposed to acid rain. Asymmetric flow field-flow fractionation (AF4), scanning transmission electron microscopy-energy dispersive spectroscopy (STEM-EDS) and ultrafiltration were used to clarify the size distribution and elemental composition of WDCs containing PTEs. Solution dynamics of successive leaching indicate high release potential for As, Cd, and Pb depending on soil properties under long-term (∼65 years) acid rain. Both ultrafiltration and AF4 analysis show that As in leachate was mainly in the “truly dissolved” fraction, while Pb, Cu, Cd and Fe were predominantly in the colloidal fraction and their percentages increased with increasing extraction time by acid rain. AF4-UV-ICP-MS and STEM-EDS reveal that nanoparticles at 1–7 nm most likely composed of organic matter (OM)-Fe/Al(/Si) oxides composite were the main carriers of Pb, Cu, As and Cd. Lead was also verified in Fe-oxide colloids at 34–450 nm in the first extracts but disappeared in the tenth extracts. This indicates that WDC-bearing PTEs become smaller as leaching proceeds. The study indicates the quantitative description and size-resolved understanding of WDC- and nanoparticle-bound PTEs in leachates of contaminated soils subjected to long-term acid rain.