A modified method to prepare high-quality thiol-capped CdTe nanocrystals (NCs) was reported in this paper. The experimental results showed that the different molar ratios of the ligands (thioglycolic acid) to monomers (Cd2+ ions) in the precursor solution played an important role in the photoluminescence (PL) quantum yield (QY) of the as-prepared CdTe NCs. When [ligand]/[monomer] = 1.2, the maximum fluorescent emission peak appeared in the orange-red window, and the PL QY increased up to 50% at room temperature without any postpreparative treatment. In the meantime, suitable reaction conditions were in favor of the optimization of the surface structure of NCs, resulting in the relatively high PL QY from green to red. In addition, some differences between hydrothermal synthesis and traditional aqueous synthesis of CdTe NCs were discussed.