In this study, preferential sites for metal dissolution during anodic polarization were investigated for a biomedical CoCrMo alloy. As-cast and heat treated materials were compared through a combination of complementary techniques. Scanning Kelvin probe force microscopy mapping suggested the matrix areas adjacent to the carbides to be preferential sites for metal dissolution. By means of in situ electrochemical-optical microscopy it was observed that localized dissolution initiated from the matrix areas adjacent to carbides and grain boundaries in both materials at high anodic potential. By using scanning electron microscopy and transmission electron microscopy/energy dispersive spectroscopy analysis, submicron-sized carbides were found along the grain boundaries, and significant Cr depletion was detected across the grain boundaries for both materials, providing an explanation for the initiation of metal dissolution. A slightly higher metal dissolution was observed for the as-cast sample at high anodic potential, probably due to a more heterogeneous microstructure. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.056209jes] All rights reserved.