Synthesis of cadmium sulfide (CdS) nanocrystallites has been performed through the microwave (MW) assisted reaction of cadmium acetate with thiourea in N,N-dimethylformamide (DMF) in the presence of two capping agents, 1-butanethiol and 2-mercaptoethanol. Attempts were made to control the size and size distribution of the thiol capped CdS nanocrystallites by controlling the number of MW irradiations/exposures for a fixed time (duration). The prepared nanocrystallites have been characterized by UV-vis spectroscopy, FTIR, XRD, FESEM and TEM. The peak position of the absorption band of the 1-butanethiol caped CdS nanocrystals in DMF solution shifted towards longer wavelength with the increasing number of MW exposures indicating the growth of particle size. In contrast, the peak position of absorption band for the 2-mercaptoethanol capped CdS nanocrystals remained nearly at the same wavelength and only the intensity of the absorption band increased with the increasing number of MW exposures. The observed steady state photoluminescence (visible range) of the 1-butanethiol capped CdS nanocrystals in DMF solution shifted towards higher wavelength, showing a decrease in intensity, with the increase in the number of MW exposures. Whereas in the case of 2-mercaptoethanol capped CdS nanocrystals in DMF solution, the photoluminescence peak remained nearly at the same position showing a decrease in intensity with increase in the number of MW exposures. The interesting results on the size-dependent steady state and time resolved photoluminescence (PL) of the CdS nanocrystallites are discussed in the present article. Possible application of such studies in the area of biotechnology has been mentioned.