Divergent double-subduction is an important component of plate tectonics and continental growth at modern active convergent margins. However, such a process is rarely identified by deep seismic reflection (DSR) profiles, which casts doubt on its past significance. We report here a 416 km DSR profile of large dynamite shots across the Great Xing’an Range (NE China), which shows multiple arc-shaped reflections in the upper-middle crust of the Xing’an terrane, and densely layered reflection structures suggesting tectonic nappes in the lower crust. This new evidence, together with recent geological studies, indicates that the Xing’an terrane may not be a micro-continental block as previously thought, but a Paleozoic accretionary complex. In addition, there is a strong west-dipping reflection at the boundary between the Xing’an and Erguna terranes in the western DSR profile extending from the lower crust to the lithospheric mantle, suggesting that this fossil subduction zone is most likely the Toudaoqiao-Xinlin suture, which separates the Xing’an and Erguna terranes. In addition, an east-dipping strong reflection was also found in the eastern profile between the Xing’an and Songliao terranes, corresponding to the Hegenshan-Nenjiang suture at the surface. Given the newly identified crust-mantle structure, the opposite subduction zone, and other geological evidence, we propose a new model that the Xing’an terrane was developed by divergent double-subduction of the Paleo-Xing’an Ocean (part of the Paleo-Asian Ocean in the area) from ca. 500 Ma to ca. 300 Ma. Our study provides the first DSR evidence for a divergent double-subduction in the Paleozoic, which emphasizes its importance in past accretionary orogens.