A combination of Auger electron spectroscopy and temperature-programed desorption was used to characterize the growth and interaction of Pd films with positively and negatively terminated ferroelectric LiNbO3(0001) surfaces. The growth mode of vapor-deposited Pd layers at 300 K was found to be dependent on the direction of the ferroelectric polarization with layer-by-layer growth occurring on the negative (c−) surface and particle formation occurring on the positive (c+) surface. The Pd metal layers were also found to be more thermally stable on the c− surface relative to the c+ surface. These results provide another example of how the polarization orientation in ferroelectric materials affects adsorption and reaction on their exposed surfaces.