The preparation, complex magnetic properties and room-temperature magnetocaloric effect in Nd(Cu 3−x Mn x )-Mn 4 O 12 with cation distribution (Nd 3+ ) A (Cu 3−x 2+x Mn x 3+ ) A′ (Mn 1+x 3+ Mn 3−x 4+ ) B O 12 2− (x = 1 and 1.5) have been reported. Both compounds show a sharp paramagnetic-ferromagnetic (FM) transition at T C of 300 and 280 K, respectively. The substitution of Cu by Mn at the A′ site induces the emergence of a spin glass state below ≈63 K for x = 1 and ≈72 K for x = 1.5 compound. Another antiferromagnetic-like magnetic transition is also observed in both compounds at 23 and 28 K, respectively, which is discussed as the antiferromagnetic coupling between Nd 3+ at the A′ site and (Mn 3+ /Mn 4+ ) at the B site. These two compounds exhibit roomtemperature magnetocaloric effect. For a small field of 2 T, the maximum magnetic entropy changes −ΔS M are 1.5 J/kg K at 300 K and 1.4 J/kg K at 280 K, respectively. Moreover, the −ΔS M (T) curves show an asymmetric distribution, resulting in high refrigerant capacity values for both compounds. We further demonstrate the distinct roles of the A′-and B-site spins on the magnetic properties and the origin of the spin-glass-like state in double distorted perovskites Ln(Cu 3−x Mn x )Mn 4 O 12 family of compounds.