Endohedral metal fullerene are potential nanopharmaceuticals for MRI; thus, it is important to study their effect on reactive oxygen species (ROS) homeostasis. Superoxide anion radical is one of the key ROS. The reactivity of aqueous dispersions of pristine (non-functionalized) fullerenes and Gd@C82 endofullerene have been studied with respect to superoxide in the xanthine/xanthine oxidase chemiluminescence system. It was found that C60 and C70 in aqueous dispersions react with superoxide as scavengers by a similar mechanism; differences in activity are determined by cluster parameters, primarily the concentration of available, acting molecules at the surface. Gd endofullerene is characterized by a significantly (one-and-a-half to two orders of magnitude) higher reactivity with respect to C60 and C70 and is likely to exhibit nanozyme (SOD-mimic) properties, which can be accounted for by the nonuniform distribution of electron density of the fullerene cage due to the presence of the endohedral atom; however, in the cell model, Gd@C82 showed the lowest activity compared to C60 and C70, which can be accounted for by its higher affinity for the lipid phase.