Er5Si4 is a member of the R5(Si4−xGex) family of alloys, where R=rare earth metal. Many of these compounds display a strong coupling between the magnetic and crystal lattices. In the naturally layered R5(Si4−xGex) materials, inter- and intralayer interactions can be controlled by chemical and physical means; thus their physical properties can be tailored within wide limits. The Er5Si4 is unique in that the temperature dependent structural sequence is opposite that of other representatives of this family. The magnetism of Er5Si4 is reflective of its exceptional place within the series.