The employment of 2-amino-isobutyric acid, Haib, and 2-hydroxy-1-naphthaldehyde, Hnaphth, in Ni^II/Ln^III chemistry has led to the isolation and characterization of two new isostructural 3d–4f tetradecanuclear [Ni^II₆Ln^III₈] clusters (Ln = Gd^III, Dy^III), with the Dy analogue displaying temperature and frequency dependent out-of-phase signals, and the Gd analogue showing interesting magnetocaloric properties.