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Recently highly luminescent C70(CF3)10 isomer with quantum yield of 0.68 was found among trifluoromethylated fullerenes with 2–10 CF3 groups. Here we report fluorescent properties of a variety of higher trifluoromethylated fullerenes with 12–20 CF3 groups. Trifluoromethylated fullerenes were prepared by thermolysis of CF3I with C70 fullerene in a sealed ampoule at gradient heating followed by HPLC isolation of individual isomers. Highly trifluoromethylated fullerenes demonstrate moderate quantum yields up to 0.10 and varying of emission maxima in wide region of 380–630 nm dependently on CF3 group addition pattern.