Hexagonal close-packed monolayer films of unmodified C60 fullerene were, for the first time, produced successfully by using the Langmuir–Blodgett technique. The processing parameters were optimized, and the structure of these films has been investigated using scanning tunneling microscopy and atomic force microscopy. These films have great potential applications in many different fields including transparent electrodes, sensor, optoelectronic devices and photovoltaics.