The WC/WC grain boundary structure and intergranular segregation in WC-Co and WC-VC-Co cemented carbides were investigated by high-resolution transmission electron microscopy and energy dispersive X-ray spectroscopy in order to elucidate whether contiguous boundaries were present or not at the atomic level. Some grain boundaries were separated by liquid phase, while others were contiguous at the atomic level. Cobalt was found to be segregated to WC/WC grain boundaries in WC-Co. Cobalt and vanadium were co-segregated to grain boundaries in WC-VC-Co. The segregation width in both materials was about 6 nm. These results suggest that the vanadium present in contiguous boundaries acts as an effective barrier to the migration of boundaries during sintering and annealing. This could explain the grain growth inhibiting mechanism of VC added to WC-Co.