Magnetic Fe‐Bi multilayers have been, for the first time, synthesized by using electron‐beam evaporation at 140 K. The relationships between film structure and magnetic properties were investigated by means of measurements of magnetization, x‐ray diffraction, electron diffraction, and Mo¨ssbauer spectra. Films are ferromagnetic or paramagnetism, depending on Fe layer thickness,tFe. Films withtFeof about 1 nm exhibit perpendicular magnetic anisotropy while these with the thickertFehave in‐plane magnetism. Temperature dependence of magnetization in the Fe‐Bi multilayers was also studied in the temperature range of 77–600 K.