Nanocrystalline PbS-doped tetramethoxysilane (TMOS) silica xerogels are prepared by reacting lead nitrate with thiourea, followed by hydrolysis and polycondensation of TMOS in the presence of an ammonium hydroxide (NH4OH) catalyst. The effect of NH4OH/TMOS molar ratio on PbS crystallite size is studied by keeping the PbS/TMOS molar ratio constant at 0.006. The PbS/TMOS molar ratio is varied from 0.0008 to 0.08 and its effect on the optical properties of the PbS-doped xerogels is studied. The color of the xerogels varied form yellow to black by varying the PbS/TMOS molar ratio from 0.0008 to 0.08, respectively. The threshold absorption peak shifted from higher to lower wavelength with decreasing PbS/TMOS molar ratio from 0.08 to 0.0008, due to a size quantization effect. X-ray diffraction (XRD) measurements show that the crystallite size of PbS varied from 2 to 15 nm by varying the PbS/TMOS molar ratio from 0.0008 to 0.08, respectively. The effect of temperature on PbS crystallite size is also studied. It is found that with increasing temperature from 100 to 300 degrees C, crystallite size increased from 3 to 14 nm. The XRD measurements show that the PbS crystallites in TMOS xerogels have cubic rock salt structure.