We report on atomic-scale analyses using high-resolution scanning transmission electron microscopy (HR-STEM), atom-probe tomography (APT), and first-principles calculations to study grain-boundary (GB) segregation behavior of Nb 3 Sn coatings on Nb, prepared by a vapor-diffusion process for superconducting radiofrequency (SRF) cavity applications. The results reveal Sn segregation at GBs of some Nb 3 Sn coatings, with a Gibbsian interfacial excess of ~10-20 Sn atoms/nm 2 . The interfacial width of Sn segregation at a GB is ~3 nm, with a maximum concentration of ~35 at.%. HR-STEM imaging of a selected [12 ̅ 0] tilt GB displays a periodic array of the structural unit at the core of the GB, and firstprinciple calculations for the GB implies that excess Sn in bulk Nb 3 Sn may segregate preferentially at GBs to reduce total internal energy. The amount of Sn segregation is correlated with two factors: (i) Sn supply; and (ii) the temperatures of the Nb substrate and Sn source, which may affect the overall kinetics including GB diffusion of Sn and Nb, and the interfacial reaction at Nb 3 Sn/Nb interfaces. An investigation of the correlation between the chemistry of GBs and Nb 3 Sn SRF cavity performance reveals no significant Sn segregation at GBs of high-performance Nb 3 Sn SRF cavities, indicating possible effects of GB segregation on the quality (Q 0 ) factor of Nb 3 Sn SRF cavities. Our results suggest that the chemistry of GBs of Nb 3 Sn coatings for SRF cavities can be controlled by grain-boundary engineering, and can be used to direct fabrication of high-quality Nb 3 Sn coatings for SRF cavities.