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Nitrogen δ-doped GaAs superlattices (SLs) were fabricated, and their energy structures were investigated. A number of strong transition signals are observed in photoreflectane (PR) spectra in an energy range from 1.54 to 1.78 eV for SL samples in which any transitions are not observed in uniformly nitrogen-doped GaAsN with comparable nitrogen content. Both of the E+ and E- bands formed around the nitrogen δ-doped layers compose SL potentials with the conduction band of the spacer GaAs layers, resulting in the formation of multiple minibands. The energy range of the SL minibands well explains the observed transition energies in the PR spectra. The PR signal intensity ratios of the E+-related transitions to the E--related transitions for the SLs are notably large compared with those usually observed for conventional GaAsN alloys. This enhancement of electron transition associated with the E+-related bands should be advantageous as intermediate band material. Therefore, nitrogen δ-doped GaAs SLs are expected to be an excellent alternative to uniformly doped GaAsN alloys for the use in intermediate band solar cells.