Multiferroics refer to materials with two or more ferroic orders in one phase within a specific temperature range, including ferroelectricity, ferroelasticity, and ferromagnetism which have been widely used in sensors, actuators, and memory devices. Among them, hybrid perovskites exhibiting multiferroicity are generally limited to low dimensions (0D–2D). Designing 3D lead‐free perovskite multiferroics remains a challenge due to Goldschmidt's tolerance factor limitation. Here, a multiferroic perovskite (R‐3AP)RbBr3 (1; 3AP = 3‐ammoniopyrrolidinium) is successfully synthesized by introducing homochirality to the 3D ferroelectric (Rac‐3AP)RbBr3, achieving both ferroelasticity and ferroelectricity. Compound 1 undergoes a structure phase transition at 401 K belonging to Aizu notation 432F2(s), which has 12 ferroelectric equivalent polarization directions and 6 polar axes. Furthermore, 1 exhibits reversible second harmonic generation switching effects. Moreover, while the temperature varies, the reversible and rapid changes of ferroelastic domains in 1 are observed using a polarizing microscope, indicating that it is a ferroelastic material. This work provides a practical method for designing and synthesizing molecule‐based multiferroics. The work reports a 3D perovskite multiferroics (R‐3AP)RbBr3 (1) based on the 3D rubidium‐based ferroelectric (Rac‐3AP)RbBr3 by using the homochirality strategy. Compound 1 exhibits 432F2(s) ferroelectric–ferroelastic phase transition at 401 K. In addition, 1 exhibits a second harmonic generation (SHG) switch and multi‐axis ferroelectricity with a saturation polarization (Ps) value of 1.21 µC·cm−2.