With the use of sol–gel method BaTiO3–SiO2 multilayer structures were fabricated on glass or fused silica substrates employing dipping or spinning procedure. The photonic stop band was observed in the reflection and transmission spectra of the multilayer structure annealed at [Formula: see text]C. It is redshifted with an increase of the thicknesses of BaTiO3 and SiO2 layers. For structures comprising Eu-doped BaTiO3 layers of different thicknesses photoluminescence with the main band at 614[Formula: see text]nm was detected. It is characterized with the double-exponential decay with the lifetimes of about 0.5[Formula: see text]ms and 1.1[Formula: see text]ms which do not depend significantly on the photonic stop band position.