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A series of azahomofullerenes and poly(amino)fullerenes were synthesized. Photoluminescence (PL) and photovoltaic (PV) measurements were performed on the composite films of conjugated polymer MEH-PPV with fullerene derivatives to investigate the influence of an electron acceptor on the charge-transfer process between components of PV system. We found that the PL of MEH-PPV is strongly quenched by the admixture of the fullerene derivative. The efficiency in the PV device containing the blend MEH-PPV/azahomofullerene is two orders of magnitude higher than in pure MEH-PPV.