We demonstrated a simple method of fabricating large-area, few-layer graphene that involves performing femtosecond pulsed laser deposition at a relatively low temperature of 500 °C and a high pressure of 10−5 Torr using a double-layer Ni catalyst. The average thickness of the resulting graphene films was less than 3 nm, their average area was more than 1 cm2, and their electrical resistivity was only 0.44 mΩ.cm. The laser deposition process was also conducted at different laser energies, and it was observed that the quality of the few-layer graphene could be improved using a double-layer catalyst at a higher laser energy. The ejection of C clusters by breaking the C–C bonds of the HOPG through multi-photon ionization can explain the observed graphene formation characteristics. The insights may facilitate the controllable synthesis of large-area, mono-layer graphene and promote the commercialize application of the graphene.