In the post‐Moore era, 2D materials with rich physical properties have attracted widespread attention from the scientific and industrial communities. Among 2D materials, the 2D homojunctions are of great promise in designing novel electronic and optoelectronic devices due to their unique geometries and properties such as homogeneous components, perfect lattice matching, and efficient charge transfer at the interface. In this article, a pioneering review focusing on the structural design and device application of 2D homojunctions such as p–n homojunctions, heterophase homojunctions, and layer‐engineered homojunctions is provided. The preparation strategies to construct 2D homojunctions including vapor‐phase deposition, lithium intercalation, laser irradiation, chemical doping, electrostatic doping, and photodoping are summarized in detail. Specifically, a careful review on the applications of the 2D homojunctions in electronics (e.g., field‐effect transistors, rectifiers, and inverters) and optoelectronics (e.g., light‐emitting diodes, photovoltaics, and photodetectors) is provided. Eventually, the current challenges and future perspectives are commented for promoting the rapid development of 2D homojunctions.