Five different commercially available fullerenes are evaluated as hole blocking/electron transporting materials in p–i–n methylammonium lead iodide perovskite solar cells using a vacuum deposited perovskite absorber layer. A significant enhancement of the solar cell performance can be obtained by selecting a suitable fullerene derivative. Open-circuit voltages as high as 1.11 volts are obtained leading to a power conversion efficiency of 14.6%.