The formation of an energy‐barrier at a metal/molecular semiconductor junction is a universal phenomenon which limits the performance of many molecular semiconductor‐based electronic devices, from field‐effect transistors to light‐emitting diodes. In general, a specific metal/molecular semiconductor combination of materials leads to a fixed energy‐barrier. However, in this work, a graphene/C60 vertical field‐effect transistor is presented in which control of the interfacial energy‐barrier is demonstrated, such that the junction switches from a highly rectifying diode at negative gate voltages to a highly conductive nonrectifying behavior at positive gate voltages and at room temperature. From the experimental data, an energy‐barrier modulation of up to 660 meV, a transconductance of up to five orders of magnitude, and a gate‐modulated photocurrent are extracted. The ability to tune the graphene/molecular semiconductor energy‐barrier provides a promising route toward novel, high performance molecular devices.