Interfaces between carbide grains in the tungsten carbide-cobalt composite have been considered. Different techniques, such as transmission electron microscopy and energy dispersive X-ray analysis have been used to characterize the orientation relationship, the nature of the planes and the chemical composition of the grain boundaries.The cobalt concentration at WC-WC grain boundaries was determined by X-ray energy selective analysis in the TEM. Cobalt profiles were performed across low-angle grain boundaries, coincidence and general grain boundaries. Cobalt segregation was found whenever dislocations were imaged in the grain-boundary plane of a low-energy grain boundary. The segregation value was compared with the segregation ratio measured in special grain boundaries characterized by a coincidence site lattice.