The high temperature reaction of C60 with silver(I) trifluoroacetate followed by 500°C sublimation and HPLC purification has led to the characterization of the trifluoromethyl‐[60]fullerenes 1,4‐C60(CF3)2, C s‐C60(CF3)4, C 1‐C60(CF3)4, and C 1‐C60(CF3)6 by EI‐MS and 19F NMR. The compounds C 1‐C60(CF3)4 and C 1‐C60(CF3)6 were obtained with 90+% compositional purity. A sample of C60(CF3)2 also contained ca. 15–20% of a C s‐symmetry isomer of C60(CF3)4. The structural assignments are based on calculations at the AM1 and DFT levels of theory.