We report on molecular beam epitaxial growth of Si doped, single and multiple quantum well structures. We have examined the effects of growth parameters such as substrate temperature, group V/III ratio, and intentional and unintentional impurities, on the electrical and optical properties of the quantum wells structures. Capacitance–voltage and secondary ion mass spectrometry analysis of the structures reveal that the net density of electrically active carriers in the wells is controlled by the number of acceptor states in the AlGaAs barrier. We have assigned the source of the acceptor state to the presence of oxygen in the AlGaAs barrier. We observe that the strength of the intersubband optical absorption from the quantum wells increases linearly with the Si‐doping in the well. Photoluminescence measurements indicate that for a given substrate temperature, a lower V/III ratio results in higher quality quantum well.