The free electron laser (FEL) of 450 or 500 nm was irradiated onto the pressed C60 powder in vacuum. The grains with μm-order were observed showing the colors of blue, purple, yellow, and white in optical microscope images. The Ag(2) derived mode around 1460 cm−1 in Raman spectra was observed from the grain, indicating the polymerization. The 100 μm-length grain was obtained just after dissolving the FEL irradiated specimens into the toluene and evaporating it. In order to expand the scale of C60 polymer grains and to obtain an amorphous C60 polymer, the FEL irradiation was carried out in solution to reduce the directivity for polymerization. Although polymerization was not promoted in C60 precipitation in supersaturated solution due to low density of C60, the precipitation grown with the liquid-liquid interfacial precipitation (LLIP) method showed the 1454 cm−1 Ag(2) derived mode in addition to the peaks around 1460 cm−1 in toluene. In m-xylene with LLIP method, in a whole area of C60 pillar-grains, polymerization was confirmed by the Raman analysis.