Off-axis electron holography in a field-emission-gun transmission electron microscope and electron dynamic simulation is used to determine the mean inner potential of copper. The phase shift of object wave versus specimen thickness is calculated up to 30 nm using electron dynamic formula, and the sample thickness is decided by match of the experimental and calculated phase shift. Based on the measured phase shift, the calculated mean inner potential of Cu is 21.2 V, which agrees with the reported values within the experimental error.