Many of the functional properties of graphene heavily depend on its morphology. Here we systematically and computationally investigate the mechanistic and quantitative role of different surface functionalized dopants on the architectural variation of nanoscale graphene by chemical functionalization. An intriguing correlation between electron orbital occupancy of doped atoms and the resultant folding angle of graphene sheet is established. Meanwhile, we demonstrate that density of doped foreign atoms adds the dimensionality of design space for regulating the folding angles of graphene sheet, providing an invaluable way for quantitatively controlling the graphene folding and a guideline to design novel graphene-based unconventional nanodevices. (c) 2013 Elsevier B.V. All rights reserved.