The interest in ferroelectric tunnel junctions (FTJ) has been revitalized by the discovery of ferroelectricity in fluorite‐structured oxides such as HfO2 and ZrO2. In terms of thickness scaling, CMOS compatibility, and 3D integration, these fluorite‐structured FTJs provide a number of benefits over conventional perovskite‐based FTJs. Here, recent developments involving all FTJ devices with fluorite structures are examined. The transport mechanism of fluorite‐structured FTJs is explored and contrasted with perovskite‐based FTJs and other 2‐terminal resistive switching devices starting with the operation principle and essential parameters of the tunneling electroresistance effect. The applications of FTJs, such as neuromorphic devices, logic‐in‐memory, and physically unclonable function, are then discussed, along with several structural approaches to fluorite‐structure FTJs. Finally, the materials and device integration difficulties related to fluorite‐structure FTJ devices are reviewed. The purpose of this review is to outline the theories, physics, fabrication processes, applications, and current difficulties associated with fluorite‐structure FTJs while also describing potential future possibilities for optimization.