The preparation, structures and properties of 3d-4f compounds, undecanuclear [La2Ni9(Gly)12(IDA)3(μ3-OH)3][La(H2O)9][Na3(H2O)7(ClO4)3](ClO4)6·5H2O (1) and isostructural heptadecanuclear [Ln5Ni12(Gly)12(IDA)6(μ3-OH)9(H2O)3](ClO4)6·11H2O (Ln = Gd (2); Nd (3); Sm (4); Tb (5); Dy (6); Y (7)) based on mixed glycine (HGly) and iminodiacetate acid (H2IDA) ligands were described. The structure of the [La2Ni9(μ3-OH)3(IDA)3(Gly)12](3+) cationic cluster in 1 can be described as a face-shared and La-centered dioctahedron. However, the [Ln5Ni12(Gly)12(IDA)6(μ3-OH)9(H2O)3](6+) cationic clusters in 2-7 bear an onion-like {Ln5}⊂{Ni12} structure, where the trigonal bipyramid {Ln5} core is encapsulated by the outer triangular orthobicupola {Ni12} shell. Magnetic studies have been performed for these compounds, and 2 displays dominant ferromagnetic coupling and has a large magnetocaloric effect (21.8 J kg(-1) K(-1), ΔH = 7 T).