AbstractTwo new tetrathiafulvalene‐based ligands {L1 = 4,5‐bis[2,6‐di(pyrazol‐1‐yl)‐4‐pyridylmethylthio]‐4′,5′‐bis(methylthio)tetrathiafulvene, L3 = 4‐(4′‐methyl‐2,2′‐bypiridin‐4‐ylmethylthio)‐5‐(2‐cyanoethylthio)‐4′,5′‐ethylenedithiotetrathiafulvene} have been elaborated and four new lanthanide coordination complexes, namely [Dy2(hfac)6(L1)]·C6H14 (1; hfac– = 1,1,1,5,5,5‐hexafluoroacetylacetonate), [Ln(hfac)3(L2)]·CH2Cl2 {Ln = Dy (2) and Yb (3); L2 = 4,5‐bis[2,6‐di(pyrazol‐1‐yl)‐4‐pyridylmethylthio]‐4′,5′‐ethylenedithiotetrathiafulvene} and [Yb(hfac)3(L3)] (4) were isolated as single crystals. The lanthanide ions adopt an N3O6 nine‐coordination with either a spherical tricapped trigonal prism (D3h) or spherical capped square antiprism (C4v) as coordination polyhedra in complexes 1–3. In 4, the YbIII ion adopts an N2O6 eight‐coordination with a square antiprism (D4d) coordination sphere. The photophysical properties of the ligands L1 and L3 were studied in both solution and solid state and rationalised by time‐dependent density functional theory. Complex 2, in which the DyIII ion has the most regular C4v symmetry, behaves as a field‐induced single‐molecule magnet.