The photoluminescence associated with silicon donors in GaAs/AlGaAs multiple quantum wells was studied at very low laser excitation intensity. Under these conditions two new impurity related features are resolved, at energies below and above the previously reported impurity photoluminescence feature. We provide a new interpretation for the observed spectra. With this assignment, binding energies of donors at the centers of the wells agree with values deduced from far-infrared magnetoabsorption experiments as well as with calculated values.