Pentamethyl-monohydro[60] fullerene C60Me5H has been synthesized through five-fold addition of methylcopper reagent to C-60. The anion C60Me5- generated by deprotonation of C60Me5H forms organometallic complexes with K+ and TI+ ions with stronger metal-carbon interaction than that in the corresponding pentaphenylated ligand C60Ph5-.