Amorphous and crystalline sputtered Tb/Fe multilayers were annealed at different temperatures in a high-vacuum furnace and investigated at 300 K by x-ray diffraction and conversion electron Mössbauer spectrometry in order to study the effect of annealing on the structural and magnetic properties. At low annealing temperature, we have evidenced an enhancement of the perpendicular magnetic anisotropy due to a demixing process which sharpens the interfaces. At intermediate annealing temperatures, the mixing of layers progressively destroys the layered structure and, finally, the sample exhibits magnetic properties of the corresponding amorphous alloy. At higher temperatures, the crystallization of bcc-Fe and hcp-Tb is observed.