Type-II GaAs/AlAs multiple-quantum well samples groan by low-pressure metal-organic vapour-phase epitaxy have been investigated. The layered structures consist of 50 periods of either 2 monolayers (ML), 4 ML. 5 ML, 6 ML, or 7 ML GaAs embedded in 28 ML AlAs. Using (100) GaAs substrates 6 degrees misoriented towards the nearest (111)B plane monolayer steps at the AlAs/GaAs/AlAs interfaces with regular terrace widths (2.7 nm) can be seen by high-resolution transmission electron microscopy. In the photoluminescence spectra even at room temperature type-I luminescence is found to be dominant. The peak wavelength of this emission ranges from 620 to 440 nm and is governed by the GaAs layer thickness. The comparison of the measured transition energies with calculations based on an effective mass approach and an empirical tight-binding Green's function scheme shows good agreement. The perfect interface structure of our samples with regular distribution of monolayer steps prevents obviously the loss of photoexcited carriers from the GaAs layers to the surrounding, energetically resonant AlAs material allowing only low type-II luminescence intensity. Furthermore, for our well thicknesses 2D phonons have to be coupled with 3D electrons leading to low electron-phonon interaction.