A systematic study on the influence of the alkyl side‐chain length of C₆₀ based fullerene derivatives in polymer solar cells based on an anthracene‐containing poly(p‐phenylene‐ethynylene)‐alt‐poly(p‐phenylene‐vinylene) (PPE‐PPV) copolymer (AnE‐PV) is reported. It is shown that the alkyl side‐chain length of the fullerene derivative strongly correlates with the individual photovoltaic parameters. The most pronounced dependence on the side‐chain length is found for the fill factor, spanning the range between 50–72%, which dominantly controls in combination with the short‐circuit current the power conversion efficiency. The maximum performance of 4.8% was found for an ethyl terminated side‐chain, whereas larger alkyl groups resulted in a gradually decreasing power conversion efficiency. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012