Commonly accepted design concepts for ionic liquids (ILs) state that the constituting ions must be large and carry low, well-dispersed charges. A series of ILs based of pentadeca charged ILs with pentanuclear linear {Ln₅} units ([Ln₅(C₂H₅-C₃H₃N₂-CH₂COO)₁₆(H₂O)₈](Tf₂N)₁₅ (C₃H₃N₂ = imidazolium moiety, Tf₂N = bis(trifluoromethanesulfonyl)amide) with Ln = Er, Ho, Tm) demonstrates that these criteria are not absolute. Highly charged ions can also support IL formation, provided they are sufficiently large. Expanding the series of these unconventional, record pentadeca charged with new lanthanide representatives, led to the discovery of additional unprecedented properties for ILs: The Gd compound exhibits a strong magnetocaloric effect (MCE) in the liquid state with a maximum magnetic entropy change of −ΔS_M = −11 J⋅kg⁻¹⋅K⁻¹ at 2 K for Δμ₀H = 7 T. Albeit the Dy representative shows slow magnetic relaxation, the relaxation times are not favorable for practical application as a molecular magnet. Lastly, for both the Gd and the Y compound, phosphorescence in the seconds time scale is observed, which is, to the best of our knowledge, the longest ever reported for an IL.