The first cycles of hydrogen absorption-desorption in LaNi5-H2 and LaNi4.5Cu0.5-H2 systems were studied using Tian-Calvet differential heat-conduction microcalorimetry, volumetric measurements, and powder X-ray diffraction. The diffraction profiles were analyzed, and the microstructure characteristics of the LaNi5 and LaNi4.5Cu0.5 systems at different stages of activation were determined. The pressure-composition isotherms were plotted, and the enthalpies of phase transitions α→β and β→α were calculated. The effect of substitution on the change in the thermodynamic parameters and microstructure characteristics of the hydride-forming intermetallic compounds during activation was shown.