Achieving a periodic domain structure in ferroelectric materials to tailor the macroscopic properties or realize new functions has always been a hot topic. However, methods to construct periodic domain structures, such as epitaxial growth, direct writing by scanning tips, and the patterned electrode method, are difficult or inefficient to implement in emerging molecular ferroelectrics, which have the advantages of lightweight, flexibility, biocompatibility, etc. An efficient method for constructing and controlling periodic domain structures is urgently needed to facilitate the development of molecular ferroelectrics in nanoelectronic devices. In this work, it is demonstrated that large‐area, periodic and controllable needle‐like domain structures can be achieved in thin films of the molecular ferroelectric trimethylchloromethyl ammonium trichlorocadmium (TMCM‐CdCl3) upon the application of tensile strain. The domain evolution under various tensile strains can be clearly observed, and such processes are accordingly identified. Furthermore, the domain wall exhibits a superior piezoelectric response, with up to fivefold enhancement compared to that of the pristine samples. Such large‐area tunable periodic domain structure and abnormally strong piezoresponse are not only of great interests in fundamental studies, but also highly important in the future applications in functional molecular materials.

The electrocaloric effect (ECE) is an efficient and environmentally friendly method for solid-state refrigeration driven by an electric field. However, disregarding the ECE performance, the mass of materials also limited...