The exponentially growing works on 2D materials have resulted in both high scientific interest and huge potential applications in nanocatalysis, optoelectronics, and spintronics. Of especial note is that the newly emerged and promising family of metal phosphorus trichalcogenides (MPX3) contains semiconductors, metals, and insulators with intriguing layered structures and architectures. The bandgaps of the members in this family range from 1.3 to 3.5 eV, significantly enriching the application of 2D materials in the broad wavelength spectrum. In this review, emphasizing their remarkable structural, physicochemical, and magnetic properties, as well as the numerous applications in various fields, the innovative progress on layered MPX3 crystals is summarized. Different from other layered materials, these crystals will advance a fascinating frontier in magnetism and spintronic devices with their especially featured atomic layered nanosheets. Thus, their crystal and electronic structures, along with some related researches in magnetism, are discussed in detail. The assortments of growth methods are then summarized. Considering their potential applications, the prominent utilization of these 2D MPX3 nanoscrystals in catalysis, batteries, and optoelectronics is also discussed. Finally, the outlook of these kinds of layered nanomaterials is provided. Researches on 2D materials have resulted in both high scientific interest and huge potential for a variety of applications. Herein, the frontiers on newly emerged and promising MPX3 family are summarized, which contains semiconductors, metals, and insulators with a special layered structure and architecture. Their compelling structural, physical, chemical, and magnetic properties, as well as the potential applications are highlighted.