The material removal state, which is closely related to machining quality, is an important factor in any machining process. During the machining using a non-rotational symmetric cutting tool, scratching direction manifests significant influence on the material removal state. In the present study, the relationship between material removal mode and scratching direction was investigated during the nanoscratching process on single crystal copper using an atomic force microscopy (AFM) tip. Considering the installation angle of the cantilever and the height of pile-up, a theoretical model was developed to relate machining depth with normal load for the machining of a single groove. Experimental results revealed that the theoretical normal load model was more suitable when materials were expelled in constant chip formation with small pile-ups. In addition, based on the scratching tests in different directions, the critical included cutting angle determined whether materials were expelled in chip formation or not. The height of pile-up was also influenced by the included cutting angle during the scratching in face-forward direction; however, during the machining in edge-forward direction, the distance between the cutting swept faces formed by the lateral and front edges determined the height of pile-up. Finally, an optimal machining direction is selected based on the quality of the machined grooves, which can be used in the potential application.