The Monte Carlo simulation with the energetics described by the embedded atom method has been employed to mainly study physical behaviors of boron atoms during relaxation of the Ni3Al-x at.% B grain boundary. During relaxation of impure Ni3Al grain boundaries, we suggest that for different types of impure atoms(Mg, B, Cr and Zr atoms etc.), as the segregating species, they have the different behaviors, but as the inducing species, they have the same behaviors, i.e. they all induce Ni atoms to substitute Al atoms. Calculations show that at the equilibrium, when x(the B bulk concentration) increases from 0.1 to 0.9 , the peak concentration of B increases, correspondently, the peak concentration of Ni maximizes but the valley concentration of Al minimizes, at x = 0.5. The calculations also show the approximate saturation of Ni at the grain boundary at x = 0.5.