Functionalized mixed dihydrofullerenes C₆₀RH and C₆₀RR′ are easily obtained from reactions between C₆₀²⁻ anion and halo derivatives RX and R′X. The key step consists in the selective reaction of the intermediate [C₆₀R]⁻ ion, as soon as it is formed, with either CF₃CO₂H or R′X. This process is made possible thanks to the very fast single electron transfer (SET) reaction between C₆₀²⁻ and RX. Functionalized dihydrofullerenes C₆₀RH thus prepared are also shown to be very good starting compounds for obtaining various C₆₀RR′ derivatives.