Large area (cm2) multi-layer graphene film is synthesized in the substrate-free vapor phase. The scanning electron microscopy observation reveals that the graphene nanoflakes are either six- or five-sided, and the internal angles between adjacent sides are nearly 120 and 105, respectively. The nucleation of hexagonal and pentagonal carbon rings leads to carbonaceous nuclei, which grow into six- or five-sided nanoflakes, respectively. A wellordered and large-area graphene monolayer is formed by the interconnection of these flakes, and stacking of these monolayers results in the formation of a multi-layer graphene film. The creation of hexagonal and pentagonal carbon rings is considered to be important for the easy production of large area multi-layer graphene at large scale.