Narrow field-of-view (FOV) cameras enable long-range observations and have been often used in deep space exploration missions. To solve the problem of systematic error calibration for a narrow FOV camera, the sensitivity of the camera systematic errors to the angle between the stars is analyzed theoretically, based on a measurement system for observing the angle between stars. In addition, the systematic errors for a narrow FOV camera are classified into "Non-attitude Errors" and "Attitude Errors". Furthermore, the on-orbit calibration methods for the two types of errors are researched. Simulations show that the proposed method is more effective in the on-orbit calibration of systematic errors for a narrow FOV camera than the traditional calibration methods.