High grade germanium process streams from natural resource reserves are converted to germanium tetrachloride which is purified and hydrolyzed to chemical grade germanium dioxide. Germanium tetrachloride is a corrosive, non-inflammable colourless liquid with a suffocating odour; it fumes in contact with humid air. Germanium tetrachloride hydrolyses in water in order to form hydrogen chloride and germanium dioxide. Selective homogeneous pyrolysis of organic impurities in germanium tetrachloride yielding lower molecular weight and easily separable products can be accomplished by a cw CO2 laser-photosensitized reaction. Germanium tetrachloride is used as a doping agent in the core of a silica glass optical fiber to increase the refraction index, allowing guidance of optical data through the fiber. To support optimal transmission a high purity germanium tetrachloride is critical. Low concentrations of hydrogen bonds and metallic impurities are our standard.