Transmittance measurements on various single crystal ferroelectric and dielectric materials, BaTiO(3), SrTiO(3), LiNbO(3), LiTaO(3), (PbMg(1/3)Nb(2/3)O(3))0.73-(PbTiO(3))0.27, LaAlO(3), and Bi(4)Ge(3)O(12), over a broad millimeter-wave (MMW) frequency range have been performed. Frequency dependence of the complex dielectric permittivity has been measured in the MMW region using high-power sources for the first time, using a free-space, quasi-optical MMW spectrometer equipped with high-power backward wave oscillators (BWOs) as sources of coherent radiation, tunable in the range from 30 to 120 and 180 to 260 GHz. These results are compared with MMW permittivity of these materials obtained by other methods as well as to RF, microwave, and optical frequency permittivities for all the materials tested. The effects of both crystallographic orientation and quality of the surface polishing of the crystals have been examined. Uncertainties and possible sources of instrumentation and measurement errors related to the freespace MMW technique are discussed. This work demonstrates that precise MMW permittivity data can be obtained even on relatively small and thin crystals of different surface conditions and orientations using the high-power BWO-based quasioptical approach.