TiTe 3 O 8 has been recognized as an excellent acousto-optic crystal with isotropic optical properties. In this work, the TiTe 3 O 8 crystal with sizes reaching up to 55 × 32 × 40 mm 3 was grown by the top-seeded solution growth method. The full width at half maximum of a high-resolution X-ray diffraction is 38 arcsec. A fiber-coupled acousto-optic device with polarization ability is successfully designed and fabricated based on the TiTe 3 O 8 crystal. The rise time, insertion loss, and on−off extinction are determined to be 36 ns, 1.8 dB, and 58 dB, respectively, which are better than those of TeO 2 devices. The polarization extinction ratio is about 19 dB. An actively Q-switched ytterbium-doped all-fiber laser operating at 1060 nm was successfully realized. The results show that the TiTe 3 O 8 acousto-optic modulator is a potential Q-switch for all-fiber lasers.