It is challenging to determine domain wall pinning energy and magnetic anisotropy since both coherent rotation and domain wall displacement coexist during magnetization switching process. Here, angular dependence anisotropic magnetoresistance (AMR) measurements at different magnetic fields were employed to determine magnetic anisotropy constants and domain wall pinning energy of Fe/MgO(001) ultrathin film. The AMR curves at magnetic fields which are high enough to ensure the coherent rotation of magnetization indicate a smooth behavior without hysteresis between clockwise (CW) and counter-clockwise (CCW) rotations. By analyzing magnetic torque, the magnetic anisotropy constants can be obtained. On the other hand, the AMR curves at low fields show abrupt transitions with hysteresis between CW and CCW rotations, suggesting the presence of multi-domain structures. The domain wall pinning energy can be obtained by analyzing different behaviors of AMR. Our work suggests that AMR measurements can be employed to figure out precisely the contributions of magnetic anisotropy and domain wall pinning energy, which is still a critical issue for spintronics.