The growth of a Mn-doped LiAlO₂ single crystal by the Czochralski (CZ) method and the characterization of its spectroscopy and thermoluminescence (TL) are presented. The X-ray rocking curve and chemical etching analysis show that the as-grown crystal has good crystallinity. The full-width at half-maximum (FWHM) of the LiAlO₂ (200) \omega rocking curve is 23.2 arcsec and the etching pits density of the (100) plane is (1.6–4.0)×10⁴ cm^-2. The transmission spectrum indicates that the crystal is highly transparent in the 200–1500-nm wavelength range. The emission spectrum of the crystal consists of a peak around 579 nm when excited with 428-nm light. The TL spectra show that the LiAlO₂:Mn crystal has glow peaks at 150 and 172 ℃. The change of TL characteristics of the crystal before and after thermal annealing in the air is discussed, and the effect of annealing and irradiation on the evolution of defect types is analyzed.