A new family of fullerene-based compounds, namely, soluble [60]- and [70]fullerene homodimers and the [60]/[70]heterodimer linked through 2-pyrazolino-pyrrolidino bridges, has been synthesised by simple procedures and in high yield. Electrochemical studies confirm their suitability to act as electron acceptors in combination with poly(3-hexylthiophene-2,5-diyl) (P3HT). Their optical properties in solution and in the solid state were studied. A significantly stronger absorption in [70]fullerene-containing dimers relative to [60]homodimer in solution in the visible range was observed. Furthermore, in all donor-acceptor blends studied an efficient charge transfer was observed by means of photoluminescence (PL), photoinduced absorption and light-induced electron spin resonance spectroscopy. The [70]homodimer was found to be a distinctive species, being the strongest PL quencher and most efficient acceptor with the longest lifetime of the charge-separated (polaron) states. As a consequence, bulk-heterojunction solar cells based on this novel [70]homodimer blended with P3HT demonstrated the highest quantum and power conversion efficiencies of 37 and 1 %, respectively, compared to those of [60]fullerene dimers.