The amino-functionalized cage-opened [60]fullerene derivatives were synthesized by reactions with phenylenediamine. In this reaction, the diamine undergoes direct addition to the α,β-unsaturated carbonyl moiety. Further C-C bond scission is promoted by the intramolecular SN2 reaction. These amino-functionalized derivatives possess high-lying highest occupied molecular orbital levels as suggested by electrochemical analyses. These compounds showed intense near-infrared absorption bands that tail to 900 nm, reflecting the optical transition with π-π* and charge transfer character.