Van der Waals heterostructure is formed by two-dimensional materials, which applications have become hot topics and received intensive exploration for fabricating without lattice mismatch. With the sustained decrease in dimensions of field effect transistors, van der Waals heterostructure plays an important role in improving the performance of devices because of its prominent electronic and optoelectronic behavior. In this review, we discuss the process of assembling van der Waals heterostructures and thoroughly illustrate the applications based on van der Waals heterostructures. We also present recent innovation in field effect transistors and van der Waals stacks, and offer an outlook of the development in improving the performance of devices based on van der Waals heterostructures. Crystals 2018, 8, 8 2 of 23bond and trap state on the surfaces [6], monolayer are free of these disadvantages (Figure 1a,b) and exhibit extraordinary electronic and optoelectronic properties. Additionally, without free dangling bonds, the interface between neighbor 2DLM layers are assembled by van der Waals forces, which is much weaker than chemical bond force. Therefore, the van der Waals heterostructure can be easily isolated by exfoliation with the help of taps [7]. Although some highly disparate materials have a great lattice mismatch in creating heterostructure, those can be assembled together by van der Waals force. This allows diverse 2DLMs to construct various van der Waals heterostructures (vdWHs) with completely novel properties and functions. Crystals 2018, 8, 8 2 of 22 In general, heterostructures formed by 2DLM monolayers are assembled by covalent bond force within layers and stacked together by van der Waals force between layers. Thus, there is no free dangling bond between 2DLM layers. In contrast to typical nanostructures persecuted by dangling bond and trap state on the surfaces [6], monolayer are free of these disadvantages (Figure 1a,b) and exhibit extraordinary electronic and optoelectronic properties. Additionally, without free dangling bonds, the interface between neighbor 2DLM layers are assembled by van der Waals forces, which is much weaker than chemical bond force. Therefore, the van der Waals heterostructure can be easily isolated by exfoliation with the help of taps [7]. Although some highly disparate materials have a great lattice mismatch in creating heterostructure, those can be assembled together by van der Waals force. This allows diverse 2DLMs to construct various van der Waals heterostructures (vdWHs) with completely novel properties and functions.