Unsymmetric dumbbell molecules based on N‐methylpyrrolidine[60]fullerene, oligothienylenevinylenes (nTV; n=2, 4), and N‐methylpyrrolidine[70]fullerene, namely, C60‐nTV‐C70 were synthesized and their photophysical properties were studied. In nonpolar solvents, photoinduced energy‐transfer process predominantly takes place from the singlet excited state of nTV to C60 and C70, as was confirmed by time‐resolved emission and transient absorption spectroscopy. In polar solvent, charge‐separation processes take place instead of energy transfer. The generated charge‐separated radical‐ion pairs decay to the neutral molecules by a fast charge‐recombination process; for n=4, a rate constant of 2×107 s−1 and lifetime of 50 ns were evaluated.