In the present work, the microstructural modifications of the Hf insert in plasma arc cutting (PAC) electrodes operating at 250 A were experimentally investigated during first cycles, in order to understand those phenomena occurring on and under the Hf emissive surface and involved in the electrode erosion process. Standard electrodes were subjected to an increasing number of cutting cycles (CCs) on mild steel plates in realistic operative conditions, with oxygen/air as plasma/shield gas. Microstructural analysis was performed for each electrode at different erosion stages by means of scanning electron microscopy (SEM) equipped with energy dispersive spectroscopy (EDS) and Raman spectroscopy. Electrodes cross sections were also observed by means of optical microscopy (both in bright field and in reflected polarised light) after chemical etching. In the insert, three typical zones were found after cutting: monoclinic HfO2 layer; thermally-modified transition zone with O-2-Hf solid solution; unmodified Hf. The erosion cavity and the oxide layer thickness increase with the number of cutting cycles. Macrocracking was observed in the oxide layer, while microcracking and grain growth were detected in the remelted Hf. Moreover, detachment was found at the Hf/Cu interface. Based on thermodynamics and kinetics of the Hf high temperature oxidation, conclusions can be drawn on the erosion mechanism involved. (c) 2012 Elsevier B.V. All rights reserved.