X-ray photoelectron spectroscopy (XPS) has been used to investigate grain boundary diffusion of Cu and Cr through 1000 Å thick Co films in the temperature range of 325°C to 400°C. Grain boundary diffusivities were determined by modeling the accumulation of Cu or Cr on Co surfaces as a function of time at fixed annealing temperature. The grain boundary diffusivity of Cu through Co is characterized by a diffusion coefficient, D0gb, of 2 × 104 cm2/sec and an activation energy, Ea,gb, of 2.4 eV. Similarly, Cr grain boundary diffusion through Co thin films occurs with a diffusion coefficient, Do,gb, of 6 × 10-2cm2/sec and an activation energy, Ea,gb of 1.8 eV. The Co film microstructure has been investigated before and after annealing by x-ray diffraction and transmission electron Microscopy. Extensive grain growth and texturing of the film occurred during annealing for Co deposited on a Cu underlayer. In contrast, the microstructure of Co deposited on a Cr underlayer remained relatively unchanged upon annealing. Magnetometer Measurements have shown that increased in-plane coercivity Hc, reduced remanence squareness S, and reduced coercive squareness S* result from grain boundary diffusion of Cu and Cr into the Co films.