In this work, a novel method was developed for the simultane- ous determination of different volatile elements (refractory Cr, medium volatile Cu, and easily volatile Cd) in high purity zirco- nium dioxide (ZrO2) by in situ matrix removal and electrother- mal vaporization inductively cou- pled plasma mass spectrometry (ETV-ICP-MS). A polytetrafluoro- ethylene slurry (PTFE) as a chem- ical modifier not only enhanced the difference in the volatility between the analytes and the matrix for in situ matrix removal, but also results in their similar vaporization behaviors of the different volatile elements (Cr, Cu, and Cd) for their simultane- ous determination. Under opti- mum operating conditions, the detection limits (DLs) for Cr, Cu, and Cd were 2.5, 9.8, and 3.4 ng g-1 with relative standard devia- tions (RSDs) of less than 6.2%, respectively. The calibration graphs of the analytes were linear over three orders of magnitude. This method was applied to the simultaneous determination of the different volatile elements Cr, Cu, and Cd in high purity ZrO2, and the results were in good agreement with those obtained by conventional pneumatic nebu- lization (PN) ICP-MS after separa- tion of the matrix with a solvent extraction procedure.