ZnSe layers of various thickness were grown on (001) GaAs substrates, using InxGa1-xAs or Al1-xGaxAs as buffer layers by molecular beam epitaxy and were studied by high-resolution x-ray diffraction. The principal structural characteristics of ZnSe layer and buffer layer were determined using several reflections, such as (004) and two pairs of coupled asymmetric reflections, namely (224), (-2-24) and (115) (-1-15). In order to evaluate their validity, the experimental data obtained from these reflections were handled by means of two known expressions found in the literature. We have found the relaxation process of ZnSe layers is well described by a geometrical model including the thermal strain and small strain due to work hardening. The relaxation process is faster for ZnSe grown on ternary buffer layers despite the fact that, some buffer layers are pseudomorphically grown to the substrate; therefore we conclude that not only the lattice mismatches have effect on the relaxation process but also the surface state of the buffer layer has an influence in this process.