Severe back interface recombination still impedes the enhancement of device performance in Sb 2 S 3 solar cells, primarily due to a plethora of defects derived from suspended bonds at the rear surface of Sb 2 S 3 . In contrast to the conventional physical absorption method (i.e., Sb 2 S 3 /Spiro-OMeTAD), herein, we develop a novel strategy involving cation exchange-assisted hot injection for the in situ anchoring of PbSe nanocrystalline structures to the surface of Sb 2 S 3 . This process successfully establishes a deeply buried back interface, thereby creating a robust chemically bonding bridge for facilitating smooth carrier transfer. Additionally, the energy level arrangement has been tailored by the quantum size effect of PbSe particles to mitigate band offsets at the back interface. Consequently, the decent PbSe substantially reduces the density of surface defects from 2.44 × 10 16 to 9.8 × 10 15 cm −3 , leading to an effective suppression of nonradiative recombination as supported by the reduction in the surface photovoltage. Ultimately, the power conversion efficiency of Sb 2 S 3 solar cells based on the ITO/TiO 2 /CdS/Sb 2 S 3 /PbSe/C/Ag architecture is elevated from 6.78 to 7.34%, representing the highest efficiency achieved for fullinorganic Sb 2 S 3 solar cells to date. This construction tactic of the deeply buried back interface sheds light on the pursuit of highly efficient Sb 2 S 3 solar cells.