The photovoltaic effect in crystals with selenite structure is revealed and researched in the article. The photovoltaic coefficient K14 = 210-10Аsm(W)-1 at the temperature 133 К at illumination by light with wavelength X = 500 nm for Bi12TiO20 is identified. Some experimental and physical basics of the photovoltaic effect in crystal with selenite structure are reviewed. The research shows that the photovoltaic effect should also appear in other crystals with the selenite structure. The possibility of use of the photopiezoelectrics with the selenite structure in holographic record is shown.