AbstractPhotorefractive Bi12TiO20 single crystals of high optical quality were grown in a resistive heating furnace from high temperature nonstoichiometric (10:1) solutions of Bi2O3 and TiO2 at pulling rates 0.3–0.8 mm/h at rotation 20–30 rpm along the <001> and <011> axis. Powder X‐ray analysis, Laue method, and electron‐probe microanalysis were used for characterization. BTO crystals have the bcc structure of sillenite type with a0 = 10.178(8) Å. The chemical composition of the crystals can be written down as Bi12.1 ± 0.2Tio0.96 ± 0.09O20.1. Natural optical activity ρ of BTO crystals is 6.3 ± 0.2 deg/mm at λ = 0.633 μm and 11.9 ± 0.2 deg/mm at λ = 0.5145 μm, optical absorption coefficient α = 0.42 ± 0.04 cm−1 at λ = 0.633 μm and linear electro‐optic coefficient r41 = r52 = r63 = 5.3 pm/V. Fanning effect in the “fiber‐like” BTO sample was studied and double phase conjugation with conversion efficiency up to 8% was observed in a wide range of incidence angles of the pump at λ = 0.633 μm for 2 × 3 mW input light power.