▎ 摘　　要

Manipulating the crystal orientation of emerging 2D materials via chemical vapor deposition (CVD) is a key premise for obtaining single-crystalline films and designing specific grain-boundary (GB) structures. Herein, the controllable crystal orientation of graphene during the CVD process is demonstrated on a single-crystal metal surface with preexisting atomic-scale stair steps resulting from dislocation slip lines. The slip-line-guided growth principle is established to explain and predict the crystal orientation distribution of graphene on a variety of metal facets, especially for the multidirectional growth cases on Cu(hk0) and Cu(hkl) substrates. Not only large-area single-crystal graphene, but also bicrystal graphene with controllable GB misorientations, are successfully synthesized by rationally employing tailored metal substrate facets. As a demonstration, bicrystal graphenes with misorientations of approximate to 21 degrees and approximate to 11 degrees are constructed on Cu(410) and Cu(430) foils, respectively. This guideline builds a bridge linking the crystal orientation of graphene and the substrate facet, thereby opening a new avenue for constructing bicrystals with the desired GB structures or manipulating 2D superlattice twist angles in a bottom-up manner.