decent biocompatibility over other nanomaterials. [5] However, the PLQYs of most NIR-II emissive Ag 2 S QDs are limited to less than 20%. [5,6] Therefore, it is still a great challenge to significantly improve the PLQY of Ag 2 S QDs.The PL performance of QDs is attributed to the recombination radiation of localized excitons (electron-hole pair). However, nonradiative Auger recombination, arising from the escape of photoexcited carriers to the QD surface, leads to PL quenching. [7,8] One of the alternative strategies to improve the optical properties of QDs is the heteroatomic doping. [9] Through alloying heavy metal atoms (e.g., Pb, Au) into silver chalcogenide, nonradiative recombination of the excitons can be well prevented, and thus achieving high PLQYs of more than 30%. [10,11] Notably, a recently reported case of alloyed AgAuSe QDs has achieved a high PLQY of 65.3% at 978 nm emission. [11] These cation doping strategies probably suppress cation vacancies and crystal defects resulted from the high mobility of Ag + . [12] Undercoordinated surface atoms with dangling bonds can produce surface traps, which become sites for nonradiative recombination and quench PL. [13,14] Therefore, another representative strategy is the passivation of the QD surface with thick and robust inorganic shells or appropriate surface ligands to suppress the surface trap states. [7,[15][16][17] For example, the coating of ZnS shell on the Ag 2 S QDs has been applied to reduce surface defects. [18] However, these methods have failed to achieve a high PLQY due to the large lattice mismatch (approximately 16%) between Ag 2 S core and ZnS shell. [19] Interestingly, the surface passivation of Ag 2 S QDs with Zn−thiol or Cd−thiol complex ligand shell has reduced surface defects and achieved an approximately sevenfold PL enhancement on original QDs with a PLQY of 3.1%. [20] Generally, the robust bonding of ligands to the surface atoms of QDs can inhibit the nonradiative recombination, and the optical properties of QDs can be directly influenced by QDligand binding affinity due to electronic and steric effects. [13] According to the principle of hard and soft acid-base, one of the strongest bonding is between Ag + and thiolates (RS − ) ligand, as a typical combination of Lewis soft acid and soft base. The Lewis hard base ligands such as amines (RNH 2 ), carboxylates Ag 2 S quantum dots (QDs) with high photoluminescence quantum yield (PLQY) in the second near-infrared (NIR-II, 1000-1700 nm) window are urgently pursued. Halide atoms (especially chloride) have been studied as inorganic capping ligands on improving the PLQY of Cd-, Pb-based chalcogenide QDs; however, it remains a challenge to well replace the organic ligand with chloride ligand from silver chalcogenide QDs. Herein, a novel strategy to prepare Ag 2 S QDs with significant photoluminescence (PL) enhancement via chloride-mediated growth and passivation is demonstrated. The oleylamine and oleate ligands on the surface of silver-rich Ag 2 S QDs are readily replaced by chloride ligands d...