Multiple quantum well structures consisting of alternating layers of two crystalline organic semiconductors, namely, 3,4,9,10 perylenetetracarboxylic dianhydride (PTCDA) and 3,4,7,8 naphthalenetetracarboxylic dianhydride (NTCDA), have been grown by organic molecular beam deposition. The individual layer thicknesses in the multilayer samples were varied from 10 to 200 A˚. X‐ray diffraction and birefringence data show that there is a strong structural ordering in all layers, as well as across large spatial distances along the sample surface. Thus, the growth is ‘‘quasi‐epitaxial’’ even though the PTCDA and NTCDA crystal structures are incommensurate. From the optical absorption spectra, it was found that the lowest energy PTCDA singlet exciton line shifts to higher energy with decreasing layer thickness. Comparison of these results with a quantum mechanical model based on exciton confinement in the PTCDA layers is proposed to describe the energy shift.