The coalescence extraction system was developed for rapid, efficient, and selective separation of zirconium and hafnium from an aqueous solution containing alkali, alkaline earth, and transition metal ions. Extraction was based on the coalescence properties of glutaronitrile in combination with the aqueous solution at elevated temperature from a homogeneous solution. In the next step, a significant temperature reduction (temperature-induced phase separation) was used to enter the spinodal to form the two phase’s regions. The particle-size distribution at coalescence temperature was measured by a laser particle-size analyzer. Metal separation could be completed in a single operation lasting only 2 min with the extraction efficiency of more than 90%. The extractability in the coalescence extraction was comparable to that of traditional methods and was feasible for rapid separation of zirconium and hafnium. The mechanism of extraction was proposed depending on the hydrolysis and polymerization of these ions and the temperature of extraction.