Dynamic variations in chemical composition and size distribution of dissolved copper (Cu) along the river-sea interface in the Yellow River Estuary (China) were investigated. On average, ~64% and ~8% of bulk dissolved Cu (<0.45 μm) were partitioned in the <1 kDa fraction and 1–100 kDa, respectively. The other 28% were in the 100 kDa–0.45 μm colloids, which indicates that this fraction may dominate the overall morphology of colloidal Cu. The <3 kDa Cu fraction was susceptible to environmental parameters and the >3 kDa fraction was related to the behavior of dissolved organic carbon. 1–100 kDa Cu migrated more violently than >100 kDa Cu and tended to be a stable polymer, with stability increasing towards the sea. The source of <1 kDa Cu was complex and may be supplemented by the decomposition of small molecular colloids and the addition of the sediments or particles ligands.