The effect of pressure on the kinetics of grain boundary (GB) segregation in the Cu–50 at. ppm Bi alloy has been studied. It was found by means of Auger electron spectroscopy that at a temperature of 1173 K the segregation level decreases from 2 to 1.5 monolayer as the pressure increases from 0.01 to 1.2 GPa. This behavior was explained by considering the physical parameters controlling kinetics and thermodynamics of GB segregation. A simplified model based on dislocation pipe diffusion, proposed previously and discussed in more details in this work, was used to calculate the non-equilibrium GB segregation during cooling under high pressure. The pressure effect on bulk diffusion is responsible for the suppression of GB segregation, while the pressure effect on the phase stability in Cu–Bi alloys provides a negligible contribution on GB segregation in the pressure range studied.