An X-ray diffraction method that uses a slightly diverging (3) beam and maximally attainable diffraction angles B (as large as 77°) was developed to study quantum wells (QWs) with widths of 5-8 nm separated by wide (100-220 nm) barrier layers. The advantage of this method compared to the use of a parallel beam is an increase by two orders of magnitude in the intensity of the beam incident on the sample and an increase in the probability of diffraction for all QWs as a unified single crystal. It is found that the growth on GaAs substrates misoriented by 10° from the (001) plane in the II direction brings about monoclinization of crystal lattices of the QW layers and barrier layers in opposite directions. Inhomogeneity of composition over the thickness of each well is observed. In the case of growth of a ZnSe/ZnMgSSe structure in which the layers have a crystal-lattice period close to the lattice period of the GaAs substrate, the QWs are inhomogeneously doped with elements from the composition of the barrier layers. The inhomogeneity of QW composition observed in the growth of mismatched layers in ZnCdSe/ZnSSe and ZnCdS/ZnSSe structures is caused by the fact that mismatch between the lattice parameters of QWs and barriers stimulates the growth of self-consistent compositions; this occurs due to a decrease in the Cd concentration in the Zn1-x Cd x Se QW in the initial stages of growth compared to the Cd concentration in the flow of gases and an increase in the Zn concentration in the Cd1-x Zn x S QW at small values of x up to the concentration matching GaAs (x = 0.4). The mismatch stresses are partially relaxed via dislocations with the (111)II glide planes, as a result of which is observed the combination of rotation of the crystal planes of the layers and QW around the  axis and almost cylindrical bending of the entire sample around the perpendicular  axis. Mismatch between lattice parameters of the ZnMgSSe barrier layers and the substrate brings about decomposition of these layers into two phases; this decomposition is caused by thermodynamic instability of the alloy.