Inorganic-organic hybrid molecular multiferroic and magnetoelectric materials, similar to multiferroic oxide compounds, have recently attracted increasing attention because they exhibit diverse architectures, a flexible framework, fascinating physics, and potential magnetoelectric functionalities in novel multifunctional devices such as energy transformation devices, sensors, and information storage systems. Herein, the classification of multiferroicity and magnetoelectricity is briefly outlined and then the recent advances in the multiferroicity and magnetoelectricity of inorganic-organic hybrid molecular materials, particularly magnetoelectricity and the relevant magnetoelectric mechanisms and their categories are summarized. In addition, a personal perspective and an outlook are provided.

Magnetoelectric materials with a large magnetoelectric response, a low operating magnetic (or electric) field, and a room‐temperature (or higher) operating temperature are of key importance for practical applications. However, such materials are extremely rare because a large magnetoelectric response often requires strong coupling between spins and electric dipoles. Herein, an example of a magnetoelectric composite is prepared by using a room‐temperature multiaxial molecular–ionic ferroelectric, tetramethylammonium tetrachlorogallate(III) (1). Investigation of the magnetoelectric effect of the magnetoelectric laminate composite indicates that its room‐temperature magnetoelectric voltage coefficient (αME) is as high as 186 mV cm−1 Oe−1 at HDC = 275 Oe and at the HAC frequency of ≈39 kHz, providing a valid approach for the preparation of magnetoelectric materials and adding a new member to the magnetoelectric material family.

A novel bent ligand-pillared three-dimensional Hofmann-type metal-organic framework, [Fe(Hbpt)Pt(CN)]·1/2Hbpt·1/2CHOH·5/2HO [1, Hbpt = 4,4'-(1H-1,2,4-triazole-3,5-diyl) dipyridine], was synthesized and crystallographically and magnetically characterized, which showed incomplete three-step spin-crossover behavior with a reversible three equal-step sequence of HS ↔ HSLS ↔ HSLS ↔ HSLS.