In this work, we have synthesized LaNi5/A and Mg2Ni/A (A = graphite, copper or palladium) nanocomposites. The A elements were distributed on the surface of ball milled alloy particles homogenously and role of these particles is to catalyze the dissociation of molecular hydrogen on the surface of studied alloy. Mechanical coating with graphite or palladium effectively reduced the degradation rate of the studied electrode materials. Results showed a significant broadening of the valence bands of studied nanocomposites compared to those obtained by theoretical band calculations. The reasons responsible for the band broadening of the nanocrystalline LaNi5- and Mg2Ni-type alloys are probably associated with a strong deformation of the nanocrystals in the mechanically alloyed (MA) samples. Normally the interior of the nanocrystal is constrained and the distances between atoms located at the grain boundaries expanded. The valence band spectra of the MA samples could be also broadened due to an additional disorder introduced during formation of the nanocrystalline structure.