The purpose of this work is to synthesize a three-dimension C60 polymer using photo-polymerization method. The used pristine materials were C60 precipitates prepared by a liquid-liquid interfacial precipitation (LLIP) method. The prepared LLIP material was set in the vacuum and was compressed in the anvil with the pressure of 600 MPa or 7 GPa. The 4th harmonics FEL with the wavelength of 500 nm was irradiated with macro-pulses (the pulse width of 20 µs) containing very short micro-pulses (the pulse width of 200 fs). The Raman Ag(2) peak of C60 molecules in the vicinity of 1469 cm-1 becomes broad and shifts to the lower energy region as proceeding of polymerization. Under high pressure and/or FEL irradiation the LLIP crystal revealed the large red-shift and the increment of the half width of the Raman Ag(2) peak. Furthermore the LLIP crystal mixture with iodine revealed the more distinctive red-shift, ca.13cm-1 because of highly packing of C60 molecules. The C60 molecular accession by LLIP process and/or the photo-assisted hole-doping from iodine were promising conditions to promote the photo-polymerization effectively.