High‐quality C60(111) overlayers are grown on Au(111)/Ag(111)/mica substrates and their structures studied by x‐ray diffraction. The structural evolution of these overlayers is investigated for growth temperatures from 120 to 290 °C. C60(111) overlayers undergo an in‐plane orientational reordering atTo∼150 °C. Above this temperature, the rotated and commensurate in‐plane structures coexist with each other. The rotated structures evolve from the in‐plane structures, which predominate at temperatures belowTo. ©1996 American Institute of Physics.