The reaction of ‐[MF(Metacn)]⋅ HO with Gd(NO)⋅5HO affords a series of fluoride‐bridged, trigonal bipyramidal {GdM} (M=Cr (), Fe (), Ga ()) complexes without signs of concomitant GdF formation, thereby demonstrating the applicability even of labile fluoride‐complexes as precursors for 3d–4f systems. Molecular geometry enforces weak exchange interactions, which is rationalized computationally. This, in conjunction with a lightweight ligand sphere, gives rise to large magnetic entropy changes of 38.3 J kg K () and 33.1 J kg K () for the field change 7 T→0 T. Interestingly, the entropy change, and the magnetocaloric effect, are smaller in than in despite the larger spin ground state of the former secured by intramolecular Fe–Gd ferromagnetic interactions. This observation underlines the necessity of controlling not only the ground state but also close‐lying excited states for successful design of molecular refrigerants. GermanKühlschrank‐Magnet: Labile Fluoridkomplexe sind nützliche Vorstufen für mehrkernige fluoridverbrückte 3d‐4f‐Systeme (links im Bild: Gd violett, Cr/Fe/Ga orange, F grün, O rot). Die Molekülstruktur erzwingt schwache Austauschwechselwirkungen, die, im Zusammenspiel mit leichten Hilfsliganden, extreme Änderungen der magnetischen Entropie bewirken.