Molecular perovskite materials have recently attracted extraordinary interest from the academic community owing to their excellent multifunctional properties. Nevertheless, although massive efforts have been made, molecular ferroelastics with three-dimensional (3D) perovskite structures are still rare. Herein, we report two 3D organic-inorganic hybrid perovskites [(2-hydroxy-propyl)-tripropyl-ammonium][Mn(dca)3] (1) and [(2-hydroxy-1-methyl-ethyl)-tripropyl-ammonium] [Mn(dca)3] (2) [dca = dicyanamide, N(CN)2]. The different position of the chiral center results in a tremendous difference in the properties. Compound 1 displays only one phase transition; however, intriguingly, 2 has three phase transitions and represents ferroelastic behavior with exceptional two-step switching of quadratic nonlinear optical (NLO) properties. To the best of our knowledge, this is the first molecular ferroelastic with two-step switching of quadratic NLO properties. The results demonstrate that the molecular chiral design works, and this finding opens up a new avenue to designing multifunctional molecular perovskite materials.