Evidence for solid-state diffusion (the second half of the 19th century). The first measurements of solid state diffusion (W. Roberts-Austen, 1896–1922). The first tracer experiments to determine the solid-state diffusion (G. von Hevesy, 1913–1923). The first evidence of accelerated diffusion in polycrystalline materials (1924–1935). Autoradiographic studies of grain boundary diffusion (50s of 20th century). The first quantitative experimental and theoretical studies of the “short circuiting” diffusion (beginning from 1949, D. Turnbull and R. Hoffman – General Electric Research Lab.): radiotracer serial sectioning method, the Fisher model (1951) for grain boundary diffusion, exact solutions and developments of the Fisher model (1954–1963). The progress in the experimental methods for determination of grain boundary diffusion data and results of measurements for different metallic systems (up to date). The measurements of grain boundary diffusion parameters in the B and C regimes. Grain boundary diffusion and grain boundary segregation. Nonlinear segregation effects. Structural effects of grain boundary diffusion. Diffusion in bicrystals. Diffusion in nanocrystals. Computer simulation of grain boundary diffusion. Mechanisms of grain boundary diffusion.