The plastic deformation behavior of cemented carbides is related to the WC grain boundary strength. Ab initio calculations predict that Co and Mn segregate to WC/WC grain boundaries. To experimentally study the effect of Mn, a WC-Co-Mn material was manufactured and compared to a WC-Co material. The microstructure was studied using scanning electron microscopy (SEM), including electron backscatter diffraction (EBSD). Special attention was paid to the WC grain size and the frequency of special low-energy grain boundaries. Mn was found to have negligible effect on both the WC grain growth and the fraction of WC/WC boundaries in the as-sintered material.