We report X-valley related photoluminescence emission from AlAs/Al0.44Ga0.56As multiple quantum well structures grown on (112)B GaAs substrates. The low temperature (100 K) spectra of these structures exhibit two distinct emission peaks. One peak, located at 2.049 eV, is shown to be due to direct gap Gamma-valley transitions. This peak is independent of the layer thicknesses. The second peak, believed to be due to spatially separated X-valley related transitions, depends on the layer thicknesses. The X-valley transitions are mediated by scattering wave vectors and are enhanced because of the closeness of the AlAs mole fraction in our samples to the direct-indirect crossover composition.