It is known that CH3NH3PbI3 is particularly promising for next-generation solar devices; therefore, molecular perovskite structures have recently received extraordinary attention from the academic community because of their potential in producing unique physical properties. However, although great efforts have been made, molecular ferroelectrics with three-dimensional (3D) perovskite structures are still rare. So far, reported perovskite-like molecular ferroelectrics are basically one- or two-dimensional, significantly deviating from the inorganic perovskite ferroelectrics. Thus, their ferroelectric properties have to be greatly improved to meet the requirements of practical applications. Here, we report a 3D molecular perovskite ferroelectric: (3-ammoniopyrrolidinium)RbBr3 [(AP)RbBr3], with a high Curie temperature (Tc = 440 K) beyond that of BaTiO3. To the best of our knowledge, such above-room-temperature ferroelectricity in the 3D molecular perovskite compound is unprecedented. Furthermore, (AP)RbBr3 has great potential for applications due to its high thermal stability, ultrafast polarization reversal (greater than 20 kHz), and fascinating multiaxial characteristic. This finding opens a new avenue to the design and controllable synthesis of molecular ferroelectric perovskites, where the metal ion, halogen ion, and organic cation can be easily tuned.