The structural and hydrogen storage properties of (Nd1.5Mg0.5)Ni-7-based alloys (i.e., A(2)B(7)-type) with a coexistence of two structures (hexagonal 2H and rhombohedral 3R) are investigated in this study. In both 2H- and 3R-type A(2)B(7) structures, Mg atoms occupy Nd sites of Laves-type AB(2) subunits rather than those of AB(5) subunits because Mg substitution for Nd in the AB(2) subunits more significantly strengthens the ionic bond in the system. An increase in the A-atomic radius or the B-atomic radius stabilizes the 2H structure, but a decrease in the A-atomic radius or the B-atomic radius is favorable for formation of the 3R structure. The 2H-A(2)B(7) and 3R-A(2)B(7) phases in each alloy have quite similar equilibrium pressures upon hydrogen absorption and desorption, which show a linear relationship with the average subunit volume. The hydriding enthalpy for the (Nd1.5Mg0.5)Ni-7 compound is about -29.4 kJ/mol H-2 and becomes more negative with partial substitution of La for Nd and Co/Cu for Ni but less negative with partial substitution of Y for Nd.