2D SiN honeycomb monolayer structures predicted theoretically have been the focus of interest in materials science for a long time, most recently for their semiconducting and ferromagnetic properties. Herein, by investigating metal‐organic chemical vapor deposition processes and direct heat treatment of epitaxial graphene in ammonia flow, the possibility of realizing a certain periodic 2D structure via SiN bonds under epitaxial graphene on SiC (0001) is reported. The result is of interest because it is compatible with semiconductor material deposition technologies and future use in nanoscience and nanotechnology.