Molecular dynamics simulations were performed to explore structural arrangements of nitromethane (NM) on the graphene (GRA) surface. The simulation results show that ordered and layered structural arrangements of NM are induced by the GRA surface. In the nearest layer to the GRA surface, the structural ordering is highest. The preferred orientation of NM is found, i.e. the dipole vector is parallel with the GRA surface, leading to more concentrated and higher density than bulk NM. To maximize the interactions between NM and GRA, furthermore, some NM molecules change from eclipsed structure to staggered structure. The influence of GRA on structural arrangements of NM is weakened as the distance between NM and GRA surface increases. The structural arrangements of NM trends toward disordered state of bulk NM started with the third layer.