A novel kind of quantum dots, sulfur quantum dots (S dots), is synthesized by simply treating sublimated sulfur powders with alkali using polyethylene glycol-400 as passivation agents. The synthesized S dots exhibit excellent aqueous dispersibility, eminent photostability and temperature dependent photoluminescence (PL). An "assemble-fission" mechanism is proposed for the S dots formation in which "assembling" and property "fission" are involved and contest each other. The ultimate morphologies of the S dots are dependent on the balance of the two forces. Guided by the assemble fission mechanism, weakening the assembling effect is beneficial for obtaining monodisperse S dots, which can be achieved by pretreating of sulfur powder with nitric acid. PL wavelength of the S dots has been successfully tuned between green and blue light (from 550 to 440 nm) by simply controlling reaction time. A satisfactory quantum yield of 3.8% is obtained. Significant electrochemiluminescence of the S dots is observed in an annihilation reaction. Chemiluminescence from the S dots has been observed by direct oxidation. Taking advantage of unique and inherent antimicrobial activity of the sulfur particles, it is believed that this new emerging luminescent nanomaterial is highly promising in the development of new types of optoelectronic devices and tracer for live cells, in vivo imaging and diagnostics.