Deep ultraviolet (DUV) photodetectors play important roles in the modern semiconductor industry due to their diverse applications in critical fields. Wide bandgap semiconductor Ga2O3 is considered as one promising material for highly sensitive DUV photodetectors. However, the high responsivity of Ga2O3 DUV photodetectors always comes at the expense of its response speed. Material engineering for high-quality Ga2O3 materials can optimize the photoresponse performance but at the cost of much more complex process. Structure engineering can efficiently improve the performance of Ga2O3 photodetectors based on various physical mechanisms. Owing to the increased modulation probabilities, part schemes of structure engineering even alleviate the tough requirements on Ga2O3 material quality for high-performance DUV photodetectors. This article reviews the recent efforts in optimizing the performance of Ga2O3 photodetectors through structure engineering. Firstly, photodetectors based on Ga2O3 nanostructures and metasurface structures with nanometer size effect are discussed. In addition, junction structures of Ga2O3 photodetectors, which effectively promote carrier separation in the depletion region, are summarized based on a classification of Schottky junction, heterojunction, phase junction, etc. Besides, Ga2O3 avalanche photodiodes, offering ultra-high gain and responsivity, are focused as a promising prototype for commercialization. Furthermore, field effect phototransistors, based on which the scalability and low power performance of Ga2O3 photodetectors have been well proven, are analyzed in detail. Moreover, auxiliary-field configurations with extra tunable dimensions for Ga2O3 photodetectors are introduced. Finally, we conclude this review and discuss the main challenges of Ga2O3 DUV photodetectors from our perspective.