Lead sulfide (PbS) quantum dots are promising solution-processed materials for short-wave infrared (SWIR) photodetectors due to their tunable band gap and solution processability. Phase-transfer ligand exchange is a common method to prepare quantum dot (QD) inks used in device fabrication. For large-sized PbS QDs used for SWIR detection, the conventional phase-transfer ligand exchange has been problematic due to the densely packed organic ligands and charge-neutral (100) facets. Here, we report a new strategy to carry out the efficient phase-transfer ligand exchange in large-sized QDs. Specifically, using lead acetate trihydrate (PbAc2·3H2O) as a precursor and methylammonium acetate (MAAc) as an additive in the ligand solution, we can facilitate the efficient phase-transfer ligand exchange and epitaxial growth of perovskite intermediate (MAPbI3–xAcx) on the (100) facets, resulting in a significant improvement in film quality suitable for device fabrication. The resulting photodiodes show a 2.5× enhancement in external quantum efficiency (EQE) compared to devices using QD inks obtained using the conventional method. Considering the low transmittance of the ITO electrode in the SWIR regime, our devices exhibit an internal quantum efficiency of over 90%.