In this study, we report on the synthesis of CdSe/CdS core–shell ultrasmall quantum dots (CS-USQDs) using an aqueous-based wet chemistry protocol. The proposed chemical route uses increasing concentration of 1-thioglycerol to grow the CdS shell on top of the as-precipitated CdSe core in a controllable way. We found that lower concentration of 1-thioglycerol (3 mmol) added into the reaction medium limits the growth of the CdSe core, and higher and increasing concentration (5–11 mmol) of 1-thioglycerol promotes the growth of CdS shell on top of the CdSe core in a very controllable way, with an increase from 0.50 to 1.25 nm in shell thickness. The growth of CS-USQDs of CdSe/CdS was confirmed by using different experimental techniques, such as optical absorption (OA) spectroscopy, fluorescence spectroscopy, X-ray diffraction, Fourier transform infrared spectroscopy, and Raman spectroscopy. Data collected from OA were used to obtain the average values of the CdSe core diameter, whereas Raman data were used to assess the average values of the CdSe core diameter and CdS shell thicknesses.