Intermolecular interaction is crucial to the study of molecular dynamics. Hydrogen bond, as a special molecular interaction, has been proved an important weak interaction to influence the motions of molecular in an organic system, and it could optimize or may produce ferroelectric, ferroelastic, and ferromagnetic features. However, research on the above properties realized by hydrogen‐bond engineering is relatively rare in hybrid compounds. Therefore, we want to explore whether the enhancement of ferroic properties could be achieved through the construction of hydrogen bonds in molecular hybrid systems. Here, a ferroelastic phase transition temperature range of hybrid perovskite (Me‐Hdabco)Rb[BF4]3 is significantly increased by 71 K compared with that of [Medabco‐F]Rb[BF4]3 by constructing hydrogen bonds. This work provides the way for designing functional molecular hybrid crystals. More details are given in the article by Fu et al. on page 1559—1565.