The precise syntheses of transition–rare-earth metal clusters with desired structures remain a great challenge. Herein, by utilizing SO4 2– anion released by in-situ decomposition of sodium dodecyl sulfate (SDS) as a template, a series of novel high-nuclear ity 3d-4f clusters, formulated as [Ni24Pr22(μ3-OH)31(pida)24(SO4)4 (NO3)9(CH3 COO)3]·Br4·(NO3)11· 16H 2O·25CH3OH (1, H2pida = N-phenyliminodiacetic acid), [Ni24Nd22(μ3-OH)31(pida)24(SO4)4(NO3)9(CH3COO)3 ]·Br4·(NO3)11·14H2O· 24CH3OH·(2)·and [Ni24Gd22 (μ3-OH)36(bida)24(SO4)7(NO3)3(CH3 COO) 3]·(SO4)·Br4 ·(NO3)4·31H2O 32CH3OH (3, H 2 bida = N-benzyliminodiacetic acid), have been successfully isolated. X-ray crystal structure analyses reveal that all the cationic {Ni24 RE22}cores in 1–3 possess a ball-like structure with C3v symmetry, and can be viewed as consisting of an inner {RE22} core and an outer {Ni24} shell. From 1 and 2 to 3, due to the lanthanide contraction effect, the coordina -tion numbers for rare-earth metal centers in {RE22} are different, resulting in differ-ent number of SO42– and NO3– anions to support and stabilize the skeleton structures. Meanwhile, the magnetic properties of com-plexes 1–3 were also studied. The result revealed that complexes 1–3 show antiferromagnetic /ferrimagnetic interactions, and 3 ex-hibits magneto-caloric effect at ultralow temperatures with a maximum –ΔSm (magnetic entropy change) value of 33.03 J·kg−1 ·K−1 at 3.0 K and 7 T.