Low‐cost solution‐processed lead chalcogenide colloidal quantum dots (CQDs) have garnered great attention in photovoltaic (PV) applications. In particular, lead selenide (PbSe) CQDs are regarded as attractive active absorbers in solar cells due to their high multiple‐exciton generation and large exciton Bohr radius. However, their low air stability and occurrence of traps/defects during film formation restrict their further development. Air‐stable PbSe CQDs are first synthesized through a cation exchange technique, followed by a solution‐phase ligand exchange approach, and finally absorber films are prepared using a one‐step spin‐coating method. The best PV device fabricated using PbSe CQD inks exhibits a reproducible power conversion efficiency of 10.68%, 16% higher than the previous efficiency record (9.2%). Moreover, the device displays remarkably 40‐day storage and 8 h illuminating stability. This novel strategy could provide an alternative route toward the use of PbSe CQDs in low‐cost and high‐performance infrared optoelectronic devices, such as infrared photodetectors and multijunction solar cells.