Gold geochemical provinces in China were delineated through stream sediment or catchment sediment sampling in this study. Each gold geochemical province delineated by a threshold value of 2.5 ng/g covers an area of thousands of kilometers. It is a dilemma that geochemists traditionally thought that gold could not migrate for a long distance in rivers or streams to form a large-scale geochemical anomaly due to its chemical inertness and high specific density. The quantitative spectroscopic analysis and observations under a scanning electron microscope (SEM) indicate the presence of submicroscopic gold particles (<5 μm in diameter) in large quantities, and observations under a Transmission Electron Microscopy (TEM) further suggest the presence of nanoscale gold particles (several tens of nanometre in diameter) in ores, rocks, soils and stream sediments. Particularly, submicroscopic and nanoscale gold particles less than 5 μm were only found in samples having a low gold content (<10ng/g). This result shows that geochemical provinces, delineated by a threshold value of 2.5 ng/g, are formed by long-distance transport of ultrafine gold in streams. The findings may provide direct microscopic evidence for gold migration to form geochemical provinces.