Rare earth elements (REEs) and major ions were determined in rainwater samples collected from Guiyang in the acid rain impacted zone of Southwest China. The concentrations of total dissolved and acid-soluble REEs in rainwater are higher than those of most of the world's cities as well as the local surface water. The dissolved REE concentrations are negatively correlated to pH in rainwater. This is consistent with acidification of rainwater resulting in increasing REE concentrations. Speciation calculations using the PHREEQC-Model predict that the free REE metal ion (i.e., Ln^3 +), sulfate (LnSO₄⁺), oxalate (LnOx⁺ and LnOx₂⁻) and fluoride (LnF^2 +) complexes were relatively important forms of dissolved REE. Although the contribution to rainwater acidity of oxalic acid is much lower than that of sulfuric acid, the proportion of REE-oxalate complexes is not lower than that of REE-sulfate complexes in rain waters. The rainwater is enriched in the middle REEs (MREE) compared to both the light REEs (LREE) and heavy REEs (HREE). REE-phosphate complexes, phosphatic minerals and a Fe-Mn-oxyhydroxide coating are more likely controls on the development of MREE enrichment in the rainwater. Complexation of sulfate and REE played little role in the development of MREE enrichment, even though sulfate is the most important anion in acidic rainwater. In the shale-normalized REE pattern plot, La showed a clear positive anomaly. La might have two main anthropogenic sources in rainwater. One of the important sources could be automobile emission; another main source of excess La in rainwater could be the REE fertilizer that has been widely used in the agriculture of China for approximately 30 years.