The Bi2S3 microcrystallite doped thin films and glass lumps have been successfully prepared by the sol-gel process, the size of the microcrystallite in glass heated for different times at 400 degree(s)C was decided by the method of HRTEM. The optical transmission valley shifted towards longer wavelengths with longer heat-treatment time at 500 degree(s)C in the Bi2S3 doped thin films, showing the experimental evidence of quantum size effects. The red-shift of emission peaks in luminescence spectrum excited with longer wavelength is attributed to the broad distribution of particle size in Bi2S3 doped glass. The nonlinear refractive index of the Bi2S3 quantum dots glass which is studied by the method of Z- scan gives n2 equals 3.3089 X 10-9 esu. The optical second generation (SHG) of the Bi2S3-doped glass also is observed using a Nd:YAG colliding mode locked laser.