The composites based on reactive metals (Zr, Ta, Nb, Ti) sheets explosively welded to stainless steel plates were investigated using X-ray synchrotron radiation, TEM and SEM to characterize phase transformations in near-the-interface layers. SEM and TEM investigations of the solidified melt regions unveiled amorphous and nanocrystalline non-equilibrium phases of variable chemical compositions, incorporating elements from the joined components. Phase analysis in layers near the interface carried out using high-resolution synchrotron radiation show predominantly reflections coming from the main elements of parent sheets/plates. Nevertheless, a closer look at the diffraction patterns shows the presence of reflections coming from the phases based on the two-component equilibrium phase diagrams. The measurements performed at the interface, but including only the steel plate, revealed significant amounts of α-Fe, γ-Fe and ε-Fe phases. Their appearance was attributed to the high pressure and fast cooling rates, which promoted a martensitic transformation in steel.