Graphene was prepared using a nickel catalyst pre-deposited to a fused silica substrate through the chemical vapor deposition (CVD) process including a pre-annealing stage. The critical role of hydrogen in fabricating graphene successfully was confirmed by Raman spectra. Moreover, the purity of the graphene could be improved through adequate pre-annealing by suppressing the formation of graphite nano-rods. After the optimized CVD, it was observed that carbon atoms aggregated into tiny center spots and spread along the grain surfaces of the nickel layer, in contrast to the accumulation phenomenon on the grain boundaries. Furthermore, characterizations of the multilayer graphene (MLG) adhering directly on the fused silica were carried out, which would reflect the intrinsic properties of MLG grown on a nickel film.