A novel fullerene [5:1]hexakisadduct bearing two 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) radicals and ten 1-propyl-3-methylimidazolium bromide moieties has been synthesized and characterized. Such an C 60 IL 10 TEMPO 2 hybrid has been successfully employed as a catalyst in the selective oxidation of a wide series of alcohols and is highly active at just 0.1 mol% loading. Moreover, it can be easily recovered by adsorption onto a multilayered covalently-linked SILP phase (mlc-SILP) through a "release and catch" approach and reused for up to 12 cycles without loss in efficiency. Interestingly, a catalytic synergistic effect of TEMPO and imidazolium bromide moieties combined in the same hybrid has been clearly shown.Keywords: alcohols; fullerene; ionic liquids; oxidation; TEMPO; 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO)In the last decades TEMPO-like catalysts have emerged as powerful, metal-free and environmentally sustainable alternatives in the oxidation of primary and secondary alcohols to the corresponding carbonyl compounds.[1] Nevertheless, their high price prompted scientists examine the development of supported TEMPO catalysts in order to obtain recyclable materials. Hence, TEMPO has been covalently immobilized onto various supports such as silica, [2] magnetic nanoparticles, [3] soluble [4] and insoluble [5] organic polymers, and carbon nanotubes. [6] However, although several of these materials were catalytically active and easily recyclable, they often suffer from the inherent drawback of heterogeneous catalysis, namely the reduced mass transfer that makes reactions slower than in the case of their homogeneous counterparts. [7] In this regard, very recently a new approach called "release and catch" has been highlighted. [8] In this strategy, the catalytic system is non-covalently immobilized on the support, but the catalytic moiety is released in solution over the course of the reaction and it is recaptured at the end of the reaction. In such a manner, the benefits of homogeneous (high catalytic activity and reaction rates) and heterogeneous catalysis (easy separation and recycling) are combined. Interestingly, the "release and catch" approach has found application in organometallic-based catalysts, [9] organocatalysts [10] and metal-based catalysts. [11] In the past few years, we have been engaged in the use of silica-supported ionic liquid-like phase monolayers (SILLP) and multilayers (mlc-SILP) as reversible catalyst reservoirs. Both kinds of materials were excellently employed for organocatalyst recovery and recycling [10,12] as well as in the immobilization of Pd nanoparticles for C À C coupling processes in batch [13] and in flow. [14] On the other hand, we started exploring new recyclable TEMPO-based systems: 10 mol% of ionic liquidtagged TEMPO derivatives were easily recovered with the help of mlc-SILP and recycled in up to 13 consecutive cycles with no loss in activity, [12d] whilst a series of fullerene-TEMPO derivatives with two, four and twelve TEMPO moieties can be quickly ...