The dependence of ozone generation on the types of dielectric electrode material has been investigated using an ozone generator constructed with the piezoelectric transformer developed in our laboratory. The ozone generator is based on the excitation of the dielectric barrier discharge (DBD), which has the advantage of a compact configuration for generating ozone. Four kinds of dielectric materials are prepared for dielectric barrier electrodes. Electrical properties of the DBD and the ozone generation characteristics are investigated for the different dielectric materials. Differences in the discharge mode among the barrier electrode materials are recognized and discussed on the basis of the results of the Lissajous figures and voltage-current waveforms. During the continuous running of the generator, a temporal decrease in ozone concentration is observed owing to the temperature increase inside the reactor. Although the ozone generation characteristics are influenced by many properties of dielectrics, two important factors for achieving high-efficiency ozone generation are identified in this study. One is the use of a high-thermal conductivity material for the dielectric electrode, which functions well as a heat sink for transferring the generated heat to the outside through the material. The other factor is the control of the discharge mode. Our results show that the discharge mode that is considered as Townsend-like DBD is suitable for high-efficiency ozone generation.