Electronic traps at the inorganic-organic interface of colloidal quantum dots (QDs) are detrimental to their luminescent properties. Several types of interface traps were identified for single-crystalline CdSe/CdS core/shell QDs, which were all found to be extrinsic to either the core/shell structure or their optical performance. The electron traps-presumably excess or unpassivated Cd surface sites-are shallow ones and could be readily isolated from the electron wave function of the excitons with more than similar to 2 monolayers of CdS shell. There were two identifiable deep hole traps within the bandgap of the QDs, i.e., the surface adsorbed H2S and unpassivated surface S sites. The surface adsorbed H2S could be removed by either degassing processes or photochemical decomposition of H2S without damaging the QDs. The unpassivated surface S sites could be removed by surface treatment with cadmium carboxylates. Understanding of the surface traps enabled establishment of new phosphine-free synthetic schemes for either single-precursor or successive-ion-layer-adsorption-and-reaction approach, which yielded CdSe/CdS core/shell QDs with near-unity photoluminescence quantum yield and monoexponential photoluminescence decay dynamics with 2-10 monolayers of CdS shell.