Spectral dependencies of the persistent photoconductivity in YBa2Cu3O6.4 films have been measured at room temperature over the photon energy range 1.6-3.3 eV. Obtained spectra are well described by a set of six Lorentz peaks. We suggest a model in which the observed electronic transitions are ascribed to those in basis CuO2 planes between the conduction band (being formed by five d-orbitals of Cu2+ hybridized with p(x,y) - orbitals of O2-) and upper Hubbard unoccupied (3d(x2-y2) subband.