Colloidal quantum dots (CQDs) have a large specific surface area and a complex surface structure. Their properties in diverse optoelectronic applications are largely determined by their surface chemistry. Therefore, it is essential to investigate the surface chemistry of CQDs for improving device performance. Herein, we realized an efficient surface chemistry optimization of lead sulfide (PbS) CQDs for photovoltaics by annealing the CQD solution with concentrated lead halide ligands after the conventional solution-phase ligand exchange. During the annealing process, the colloidal solution was used to transfer heat and create a secondary reaction environment, promoting the desorption of electrically insulating oleate ligands as well as the trap-related surface groups (Pb-hydroxyl and oxidized Pb species). This was accompanied by the binding of more conductive lead halide ligands on the CQD surface, eventually achieving a more complete ligand exchange. Furthermore, this strategy also minimized CQD polydispersity and decreased aggregation caused by conventional solution-phase ligand exchange, thereby contributing to yielding CQD films with twofold enhanced carrier mobility and twofold reduced trap-state density compared with those of the control. Based on these merits, the fabricated PbS CQD solar cells showed high efficiency of 11% under ambient conditions. Our strategy opens a novel and effective avenue to obtain high-efficiency CQD solar cells with diverse band gaps, providing meaningful guidance for controlling ligand reactivity and realizing subtly purified CQDs.