We have performed both semiempirical as well as ab initio density functional theory calculations in order to investigate the structural stability of highly hydroxylated C-60(OH)(32) fullerenes, so-called fullerenols. Interestingly, we have found that low-energy atomic configurations are obtained when the OH groups are covering the C-60 in the form of small hydroxyl islands. The previous formation of OH molecular domains on the carbon surface, stabilized by hydrogen bonds between neighboring OH groups, defines the existence of C-60(OH)(32) fullerene structures with some elongated C-C bonds, closed electronic shells, and large highest occupied-lowest unoccupied molecular orbital energy gaps, with the latter two being well-known indicators of high chemical stability in these kind of carbon compounds. The calculated optical absorption spectra show that the location of the first single dipole-allowed excitation strongly depends on the precise distribution of the OH groups on the surface, a result that, combined with optical spectroscopy experiments, might provide an efficient way to identify the structure of these kinds of fullerene derivatives. We found that the presence of a few coadsorbed oxygen species on the fullerene surface leads in general to the existence of C-60(OH)(32)O-x (x = 1-4) compounds in which some of the C-C bonds just below the O impurities are replaced by C-O-C bridge bonds, leading to the formation of stable carbon-opened structures in agreement with the recent experimental work of Xing et al. (J. Phys. Chem. B 2004, 108, 11473). Actually, a more dramatic cage destruction is obtained when considering multiply charged C-60(OH)(32)O-x(+/- m) (m = 2, 4, 6) species ( that can exist in both gas-phase and aqueous environments), where now sizable holes made of 9-and 10-membered rings can exist in the carbon network. We believe that our results are important if the controlled opening of carbon cages is needed and it should be taken into account also in several technological applications where the permanent encapsulation of atomic or molecular species in these types of fullerene derivatives is required.