Persistent spectral hole burning is observed for the 413 nm 4f(7)(S-8(7/2)) --> 4f(6)5d(Gamma(8)) zero-phonon transition of Eu2+ in MBE-grown superlattices of CaF2:Eu2+/CdF2 on Si(111). Possible mechanisms for the trapping of the photoionized electron are discussed in terms of the band offsets of the superlattice layers.