Atomistic structure defects such as impurity or vacancy could influence on materialsʼ properties, and therefore it is important to investigate the local atomic structures. However, chemical bonding state may be useful for the further understanding the relationship between the structure and the properties. Here, we show that atomic-resolution differential phase contrast imaging in scanning transmission electron microscopy is able to directly visualize the anisotropy of single Si atomic electric fields in monolayer graphene. Furthermore, we also investigate the atomic electric fields of Stone-Walse defects and nanoholes in graphene. Our findings open the way to directly examine the local chemistry at the structure defects in materials at atomic-scale.