Clean ZnO (0001) Zn- and (0001 ) O-polar surfaces and metal interfaces have been systematically studied by depth-resolved cathodoluminescence spectroscopy, photoluminescence, current-voltage and capacitance-voltage measurements, and deep level transient spectroscopy. Zn-face shows higher near band edge emission and lower near surface defect emission. Even with remote plasma decreases of the 2.5 eV near surface defect emission, (0001)-Zn face emission quality still exceeds that of (0001 )-O face. The two polar surfaces and corresponding metal interfaces also present very different luminescence evolution under low-energy electron beam irradiation. Ultrahigh vacuum-deposited Au and Pd diodes on as-received and O-2/He plasma-cleaned surfaces display not only a significant metal sensitivity but also a strong polarity dependence that correlates with defect emissions, traps, and interface chemistry. Pd diode is always more leaky than Au diode due to the diffusion of H, while Zn-face is better to form Schottky barrier for Au compared with O-face. A comprehensive model accounts for the metal-and polarity-dependent transport properties.