A GeS2 gel was prepared by sol-gel processing of Ge(OEt)(4) and H2S in toluene solution. The effects of H2S and germanium ethoxide concentrations, concentration ratio, and temperature on the microstructure of the prepared GeS2 gels were studied. It was found that the concentrations of the reactants had the most significant influence on primary particle size and gel morphology. The microstructure of the dried gels was characterized by nitrogen BET analysis, SEM, powder XRD analysis, and infrared spectroscopy. Results indicate that the GeS2 gels are amorphous colloidal xerogels regardless of the reaction conditions and length of aging.