We report the preparation and characterization of an attenuated total reflection (ATR) GeO2 hollow waveguide. An internally GeO2-coated silica glass tube (bore size 1.0–1.2 mm, length 1.2 m) was prepared using a homogeneous liquid phase deposition method. Kramers-Kronig analysis reveals that the GeO2 cladding material qualifies as a reflective layer (nr < 1) for the ATR hollow waveguide structure. ATR-transmission of 9.6–11.7 μm light through HE11 mode is confirmed by loss spectrum analysis of the sample. The straight and bending (30°) transmission losses for delivery of a ∼40 W CO2 laser beam (10.6 μm) are 0.56 dB/m and 1.64 dB/m, respectively.