The polymer-complexation–ultrafiltration (PCUF) technique was applied to separate trace levels of rare earth elements (REEs), including scandium, yttrium and the lanthanides, from high-salinity matrices prior to their determination by inductively coupled plasma mass spectrometry (ICP-MS). The REEs were converted into REE–polymer complexes using the water-soluble polymer polyacrylic acid (PAA) at a specified pH, retained on the ultrafiltration membrane of centrifugal filter units, and finally eluted using diluted nitric acid to achieve separation from matrices with relatively high levels of various inorganic ions, such as sodium, potassium, calcium, magnesium, and chlorine ions. Numerous factors affecting the PCUF efficiency were optimized. The optimal conditions included the addition of 30mg L−1 of PAA, a pH of 7.5, a reaction time of 40min at room temperature, and 5.0mL of 3% nitric acid (v/v) eluent. Under these conditions, the analytes were quantitatively separated and recovered, with a resulting relative standard deviation (RSD) of less than 4.0% (0.05µgL−1, n=5) and standard addition recoveries between 89.2% (La) and 95.8% (Sm) for matrices of various salinities. The blank samples for the method ranged from 0.0003µgL−1 (Dy) to 0.0031µgL−1 (Sc), and the limits of quantification (LOQs, 10σ) were between 0.0006µgL−1 (Dy) and 0.0026µgL−1 (Sc). Furthermore, the salinity of the sample exhibited no effect on the REE–polymer complex formation process. Finally, the method was successfully applied for the determination of trace levels of dissolved Sc, Y, and lanthanides in coastal and estuarine seawater samples.