The attenuated total reflectance (ATR) hollow waveguides capable of transmitting CO2 laser have attracted wide research interest due to its advantages of simple structure, no end reflection, small beam divergence and good transmission modes. In this work, GeO2 ATR hollow waveguides for delivery of CO2 laser radiations were fabricated via an acid-induced liquid phase deposition (LPD) process. GeO2 hollow waveguide samples were deposited from acidic aqueous germanate ion solutions with different GeO2 concentrations. The morphology, compactness and surface roughness of the LPD-derived GeO2 ceramic film were examined by SEM. The crystalline structure of the film sample was determined using XRD. The low-loss window of the GeO2 waveguide tube was observed by a FTIR spectrometer. We measured the transmission loss of the sample for delivery of a 10.6 µm TEM00 CO2 laser beam. The results show that the variations in loss are consistent with the quality change of the GeO2 ceramic films grown in solutions at different concentrations.