We study the process of graphene growth on Cu and Ni substrates subjected to rapid heating (approximately 8 °C/s) and cooling cycles (approximately 10 °C/s) in a modified atmospheric pressure chemical vapor deposition furnace. Electron microscopy followed by Raman spectroscopy demonstrated successful synthesis of large-area few-layer graphene (FLG) films on both Cu and Ni substrates. The overall synthesis time was less than 30 min. Further, the as-synthesized films were directly utilized as anode material and their electrochemical behavior was studied in a lithium half-cell configuration. FLG on Cu (Cu-G) showed reduced lithium-intercalation capacity when compared with SLG, BLG and Bare-Cu suggesting its substrate protective nature (barrier to Li-ions). Although graphene films on Ni (Ni-G) showed better Li-cycling ability similar to that of other carbons suggesting that the presence of graphene edge planes (typical of Ni-G) is important in effective uptake and release of Li-ions in these materials.