The unique absorption properties of the 9-hydroxyphenalen-1-one (HPHN) ligand have been exploited to obtain visible-light-sensitizable rare-earth complexes in 1:3 and 1:4 metal-to-ligand ratios. In both stoichiometries (1:3, tris, Ln(PHN)3; 1:4, tetrakis, A[Ln(PHN)4], with Ln being a trivalent rare-earth ion and A being a monovalent cation), the complexes of Nd(III), Er(III), and Yb(III) show typical near-infrared luminescence upon excitation with visible light with wavelengths up to 475 nm. The X-ray crystal structures of the tris complexes show solvent coordination to the central rare-earth ion, whereas in the tetrakis complexes, the four PHN- ligands form a protective shield around the central ion, preventing small solvent molecules from coordinating to the rare-earth ion, at least in the solid state.