A new and readily available exTTF-bis(crown ether), 1, efficiently recognizes C60 as well as C70 by means of cooperative π-π and n-π interactions. The geometrical (concave-convex) and electronic (donor-acceptor) complementarity accounts on one hand for remarkable binding strengths, with association constants reaching 10(7) M(-1) in benzonitrile, and on the other hand for lifetimes of the photogenerated radical ion pair state on the order of 45 ps.