Pentacene films have been grown on two polar zinc oxide surfaces, i.e., ZnO(0001) and ZnO(0001(-)), as well as on the mixed-terminated ZnO(101(-)0) and are characterized by means of atomic force microscopy (AFM), x-ray diffraction (XRD), and thermal desorption spectroscopy (TDS). In all cases, pentacene aggregates in an upright orientation without any evidence for the formation of an interface stabilized wetting layer. Additional films deposited on a highly-defective, oxygen-depleted ZnO(0001(-)) reveal no altered growth mode. Nearly identical optical absorption spectra have been measured for all films, thus corroborating a weak molecule-substrate interaction. Upon cooling, however, a slightly different relaxation behavior could be resolved for pentacene films on polar ZnO surfaces compared to pentacene on the mixed-terminated ZnO(101(-)0) surface.