Hetero-tetra-metallic complexes, FeNOCuLnCo (Ln = Gd, Tb, Dy), combining magnetic properties and photo-isomerism, were obtained through the rational assembly of the photo-switching nitroprusside anion FeNO with new magnetic Schiff base CuLnCo precursors. Herein, we describe the synthesis and characterisation of these compounds followed by a demonstration of their multifunctional character. Particularly noteworthy is the FeNOCuTbCo complex, one of the few examples of a photo-isomerizable single-molecule magnet (SMM) and a significant first step toward achieving synergistic properties.