The photoluminescence behavior of CdS quantum dots in initial growth stage was studied in connection with an annealing process. Compared to the as-synthesized CdS quantum dots (quantum efficiency ≅ 1%), the heat-treated sample showed enhanced luminescence properties (quantum efficiency ≅ 29%) with a narrow band-edge emission. The simple annealing process diminished the accumulated defect states within the nanoparticles and thereby reduced the nonradiative recombination, which was confirmed by diffraction, absorption, and time-resolved photoluminescence. Consequently, the highly luminescent and defect-free nanoparticles were obtained by a facile and straightforward process.