The photodielectric effect is demonstrated in Mott-insulator BaCoSiO4 with a stuffed-tridymite-type structure under irradiation of visible light at 365 nm. The real part of dielectric permittivity is enhanced by ∼300% with little increase of tan δ in a low-frequency region. Results of diffuse reflectance spectroscopy, first-principles calculations and dielectric measurements suggest that the photodielectric effect stems from a response of photo-excited electrons in an unoccupied upper-Hubbard band for 3d-orbitals of cobalt, which have significantly small mobility due to the unique configuration of Co ions in the stuffed-tridymite-type structure.