Manipulating the ligand shell of semiconducting quantum dots (QDs) has proven to be a promising strategy to enhance their photocatalytic performance for small molecule transformations, such as H2 evolution and CO2 reduction. However, ligand-controlled catalysis for macromolecules, which differ from small molecules in penetrability and charge transfer behavior due to their bulky sizes, still remains undiscovered. Here, we systematically investigate the role of surface ligands in the photocatalytic performance of cadmium selenide (CdSe) QDs in light-induced atom transfer radical polymerization (ATRP) by using thiol-based ligands with various polarities and chain lengths. A highly enhanced polymerization efficiency was observed when 3-mercapto propionic acid (MPA), a short-chain and polar ligand, was used to modify the CdSe QDs' surface, achieving high chain-end fidelity, good temporal control, and a dispersity of 1.18, while also tolerating a wide-range of functional monomers ranging from acrylates to methacrylates and fluorinated monomers. Transient absorption spectroscopy and time-resolved photoluminescence studies reveal interesting mechanistic details of electron and hole transfers from the excited QDs to the initiators and 3-MPA capping ligands, respectively, providing key mechanistic insight of these ligand controlled and QD photocatalyzed ATRP processes. The thiolate ligands were found to serve as an efficient hole acceptor for QDs, which facilitates the formation of a charge-separated state, followed by electron transfer from the conduction band edge to initiators and ultimately suppressing charge recombination within the QD.