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).