We report the results of the surface chemistry of deuterized ethanol exposed Zircaloy-4 (Zry-4) surfaces with various amount of $C_2D_5$OD exposures at 190 K. This system was examined with Auger electron spectroscopy (AES) and temperature programmed desorption (TPD) techniques. In TPD study, $D_2$ was evolved at two different desorption temperature regions accompanying with broad desorption background. The lower temperature feature at around 520 K showed first-order desorption kinetics. The high temperature desorption peak at around 650 K shifted to lower desorption temperature as the exposure of $C_2D_5$OD increased. The Zr(MNV) Auger peak shifted about 2.5 eV from 147 eV to lower electron energy followed by 300 L of $C_2D_5$OD dosing. This implies metallic zirconium was oxidized by deuterized ethanol adsorption. After stepwise annealing of the oxidized Zry-4 sample up to 843 K, the shifted Zr(MNV) peak was gradually shifted back to metallic zirconium peak position. After the sample was heated to 843 K, the oxygen content near the Zry-4 surface was recovered to clean surface level. The concentration of carbon, however, was not recovered by annealing the sample.