We successfully deposited high-quality TiN films on c-plane sapphire by using the pulsed laser deposition technique. TiN grew on sapphire with two in-plane epitaxial relationships: (111)TiN//(0001)sapphire and TiN//sapphire or (111)TiN// (0001)sapphire and TiN//sapphire. The TiN unit cell showed a ±30° in-plane rotation for sapphire. The misfit between the TiN film and the sapphire substrate was calculated by using the near coincidence site lattice approach. The deposited films were analyzed by x-ray diffraction, transmission electron microscopy, atomic force microscopy, Rutherford backscattering or channeling spectrometry, electrical, and spectrophotometric measurements. The dependence of the film's crystalline quality on the deposition temperature has been investigated. The full width half-maximum of the rocking curve of the TiN 111 peak was 0.2–0.3°. The minimum ion channeling was 5%, and the room temperature resistivity was as low as 13 μω cm.