The grain-boundary diffusion of Co in Nb has been studied by a layer-by-layer radiometric analysis in the temperature range of 723–873 K. The diffusion annealing modes corresponded to the kinetic C mode, which implies that the diffusion proceeds only along grain boundaries. The coefficients of grain-boundary diffusion of Co in Nb have been determined for several temperatures from diffusion profiles. An expression for the Arrhenius dependence of Co diffusion coefficient along the grain boundaries of Nb has been determined. The temperature dependence of coefficient of grain-boundary segregation of Co in Nb is constructedbased on the temperature dependence of coefficient of grain-boundary diffusion of Co in Nb and the data in the literature on the temperature dependence of the triple product.