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 C60IL10TEMPO2 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 multi‐layered 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.