We revisit a series of trifluoromethylated C-70(CF3)(n) compounds with n = 2-12 to provide a comprehensive comparative characterization thereof by means of a combination of physico-chemical methods. X-ray diffraction studies, including first structural determinations of the major isomers of C-70(CF3)(2), C-70(CF3)(4), and the third most abundant isomer of C-70(CF3)(8) as co-crystals with octaethylporphyrin Ni(II), produce accurate CF3 group rotation angles and intergroup F...F distances that enable more reliable F-19 NMR signal assignment based on the through-space J(FF) spin-spin coupling relation to the F...F distances. Cyclic voltammetry measurements were performed in a potential range that covers oxidation on the one end and reduction to tri-or tetraanionic states on the other. It was demonstrated that the CF3 addition patterns have marked effects on the redox potentials. A consistent set of the experimental HOMO energy values of the C-70(CF3) n molecules is reported for the first time in complement to the LUMO data, and the both sets of results were found to demonstrate good correlation with quantum-chemical DFT predictions. Most of the compounds exhibit electrochemically reversible one-electron reductions up to trianionic (sometimes even tetraanionic) state, a notable exception being C-70(CF3)(10) with irreversibility of its very first reduction. Bulk electrolysis of C-70(CF3)(12) at its 4-th reduction potential identifies CF3 detachment as the most likely cause of the observed irreversible processes yielding C-70(CF3)(11) anions as was identified by means of MALDI MS. (C) 2017 Elsevier Ltd. All rights reserved.