Provided is a method of determining a surface orientation of a single crystal wafer. The method of determining a surface orientation of a single crystal wafer using high resolution X-ray rocking curve measurement may determine a surface angle of the wafer and a direction of the surface angle using rocking curve measurement of a high resolution X-ray diffraction method and measuring a misalignment angle formed by a rotation axis of a measuring apparatus and a surface normal of the wafer and an orientation of the misalignment angle.