The employment of 2-amino-isobutyric acid, Haib, and 2-hydroxy-1-naphthaldehyde, Hnaphth, in NiII/LnIII chemistry has led to the isolation and characterization of two new isostructural 3d–4f tetradecanuclear [NiII6LnIII8] clusters (Ln = GdIII, DyIII), with the Dy analogue displaying temperature and frequency dependent out-of-phase signals, and the Gd analogue showing interesting magnetocaloric properties.