Dynamically engineering the band alignment between materials, especially 2D semiconductors, is critically important for the design of novel devices with superior functions. Here, a review of band alignment engineering in 2D heterostructures and the derived device applications, mainly outlining their potential as photodetectors, photovoltaics, and light‐emitting devices, is provided. Various approaches are summarized, through exploiting the advantages of each component and different device structure, to further improve the performances of the optoelectronic devices. The authors also provide their perspectives on future developments of photoelectric chips based on the newly designed optoelectronic devices.