We have fabricated the polycrystalline germanium dioxide film inside the quartz capillary, and make the thin film turn into nanocluster size by controlling the grads of temperature, flow speed and the proportion of reactants. It has very highly reflectivity wavelength which is at 8~11.6 micrometer. The hollow-core fibers with the film can transmit CO2 laser energy and the infrared radiation with relevant wavelength. Its loss is about 0.4~0.8 dB/m at 10.6 micrometer wavelength. The optical fibers