This Element introduces the exotic wave phenomena arising from the extremely small optical refractive index, and sheds light on the underlying mechanisms, with a primary focus on the basic concepts and fundamental wave physics. The authors reveal the exciting applications of ENZ metamaterials, which have profound impacts over a wide range of fields of science and technology. The sections are organized as follows: in Section 2, the authors demonstrate the extraordinary wave properties in ENZ metamaterials, analyzing the unique wave dynamics and the resulting effects. Section 3 is dedicated to introducing various realization methods of the ENZ metamaterials with periodic and non-periodic styles. The applications of ENZ metamaterials are discussed in Sections 4 and 5, from the perspectives of microwave engineering, optics, and quantum physics. The authors close in Section 6 by presenting an outlook on the development of ENZ metamaterials and discussing the key challenges addressed in future works.