Stabilization of different conformers of sandwich phthalocyaninates by changing the solvation environment has been demonstrated with the examples of new heteroleptic yttrium(III) and terbium(III) triple-decker complexes [(BuO)8Pc]M[(BuO)8Pc]M[(15C5)4Pc] (where M = Y or Tb, [(BuO)8Pc]2- = octa-n-butoxyphthalocyaninato ligand, and [(15C5)4Pc]2- = tetra-15-crown-5-phthalocyaninato ligand). To this end, we have performed a comprehensive crystallographic characterization of two solvates formed by the Y(III) complex with either toluene or dichloromethane. In the solvate with toluene, both pairs of Pc ligands are in staggered conformations, providing both metal cations with a square-antiprismatic environment. In contrast, in the solvate with dichloromethane, only one cation between the BuO- and 15C5-substituted ligands remains in a square-antiprismatic polyhedron, while the pair of BuO-substituted ligands switches to a gauche conformation. In both solvates, the staggered conformations are stabilized by weak interactions of peripheral substituents with solvent molecules. Detailed analysis of the 1H NMR spectra of the isostructural Tb(III) complex in aliphatic and aromatic solvents demonstrates that the stabilization of the corresponding conformations by solvation is also valid in the solution state, resulting in an increase in the axial component of the magnetic susceptibility tensor as the symmetry decreases from staggered to gauche. Thus, solvation-induced conformational switching of lanthanide trisphthalocyaninates can be used as a tool to control their magnetic properties.