provides a feasible pathway to achieving improved ductility for brittle alloys and ceramics. [9][10][11][12][13] Moreover, GBs prove to be capable of improving the minority carrier collection in polycrystalline CdTe and Cu(In,Ga)Se 2 solar cells, leading to higher efficiencies than their single-crystal counterparts by 24% and 69%, respectively. [14,15] The GB effects tend to be enhanced in 2D materials, owing to unique space dimensionality and reduced Coulomb screening. In that case, GBs can not only directly disrupt the crystalline order, but also become all surface-accessible to permit substantial interactions with external species, providing a profound opportunity to enrich 2D materials with novel attributes.GB engineering at the atomic scale results in not only robust nanostructures but also the modification of material characteristics, which is often unachievable in pristine 2D materials. High-resolution characterization images have revealed that GBs in 2D materials are constructed by well-ordered periodic arrays of dislocation cores. [16,17] Compared with point defects (such as vacancies and impurities) that are highly vulnerable to chemical passivation or thermal annealing, GBs have conserved coordination environments, which are structurally more robust and cannot be eliminated by local structural rearrangements. [18,19] The structural diversity of GBs, enabled by flexible combinations of dislocations and varied chemical makeup, [20,21] adds extra tunability to their properties. The mechanical and electronic performances of 2D materials have been shown to depend on detailed GB microstructures. [22] Novel functionalities pertaining to GBs, such as magnetic centers, [23] catalytic sites, [24] and single photon sources, [25] have been reported. Therefore, engineering 2D materials based on GBs has opened a way to achieving a range of complementary properties through structural and compositional controls.Despite encouraging researches on the GB engineering of 2D materials, the application of GBs in functional devices remains far from being deployable, largely limited by the absence of precise control over detailed GB microstructures. Moreover, the limited understanding of the formation mechanism and structure-property relationships of GBs has also retarded the progress of this field. In this review, we examine the diverse compositions and microstructures of GBs in a range of common 2D materials, from elemental (e.g., graphene, borophene, and black phosphorus) to compound ones (e.g., h-BN, MoS 2 , and ReS 2 monolayers). The kinetic growth mechanism and energy evolution of GBs against variation in The coalescence of randomly distributed grains with different crystallographic orientations can result in pervasive grain boundaries (GBs) in 2D materials during their chemical synthesis. GBs not only are the inherent structural imperfection that causes influential impacts on structures and properties of 2D materials, but also have emerged as a platform for exploring unusual physics and functionalities stemming from dra...