We have investigated the photoluminescence (PL) properties related to the mini-Brillouin-zone boundary (π point) in a (GaAs) 24 /(AlAs) 2 superlattice. In order to detect the PL from the π-point exciton that has a very fast relaxation process in momentum space, we measured time-resolved PL (TRPL) spectra with a streak-camera system. Photoreflectance spectroscopy was adopted to characterize the optical transition energies at the mini-Brillouin-zone center (Γ point) and the π point, which results in the clear observation of the heavy-hole-exciton transition in the first quantization (n = 1) miniband at the π point, H11(π), in addition to the Γ-point exciton, H11(Γ ) usually observable. We have found that PL band relevant to the H11(π) transition appears in the TRPL spectra by tuning the excitation energy to the H11(Γ ) transition. Furthermore, the H11(π)-PL band has a delay time relative to the H11(Γ )-PL band, which reflects the pileup of excitons and carriers from the Γ point to the π point in the miniband dispersion.