The radiation-impurity modification of NaF: Eu crystals results in the formation of optically active planar heterostructures with a complex set of luminescence centers, including, in particular, clusters of the Eu 2+-Eu3+ type. The luminescence spectra of Eu 2+-Eu3+ centers exhibit bands at wavelengths of 409 and 442 nm, which are associated with Eu2+ ions in nonequivalent crystallographic positions, and a band at a wavelength of 610 nm, which is attributed to Eu3+ ions. The luminescence spectra of irradiated NaF: Eu samples contain a broad band with a maximum at 506 nm due to the presence of F2 + F3+ color centers in the crystal.