A TTF‐based (TTF=tetrathiafulvalene) tridentate ligand (α‐(4′‐methyl‐4,5‐di‐n‐dodecylthylthiotetrathiafulvalene‐5′‐ylthio)‐ α′‐2,2,2‐tris(1‐pyrazolyl)ethoxy‐p‐xylene) (L) with long‐chain alkyl moieties was prepared in order to obtain a new multi‐redox active gelator based on a mixed‐metal octanuclear complex FeIII4NiII4(CN)12(tp)4(L)4(BF4)4 (1). The magnetism, electrochemistry, and gelation behavior of 1 were studied and 1,2‐dichlorobenzene solutions of 1 are shown to display thermoreversible gelation behavior at room temperature. Furthermore, the gel phase of 1 was shown to undergo room‐temperature gel‐to‐sol transformations induced by both the oxidation and reduction of the gelator complex by F4TCNQ or FeII(Cp*)2, respectively. A new heterometallic, discrete metallogelator based on an octanuclear cyanometallate {Fe4Ni4} complex, supported by long‐chain alkyl ligands with incorporated tetrathiafulvalene moieties, was synthesized. It exhibited thermoreversible gelation behavior at room temperature and redox‐mediated gel‐to‐sol transitions.