We report the effect of ion beam mixing of Ni/Bi multilayers using 100MeV Au ions as a function of irradiation fluences. X-ray diffraction study reveals the higher magnitude of NiBi3 and NiBi phases compared to elemental Ni and Bi after ion irradiation. We observe an evolution of grainy structures to a molten-like surface with increasing ion fluences. These features were also reflected in the Rutherford Backscattering spectrometry spectra, in terms of the enhanced mixing with increasing ion fluences. The experimental findings were understood on the basis of inelastic thermal spike model calculations.