An X-ray prism for the extraction of a specific harmonic of undulator radiation is proposed. By using the prism in a grazing incidence geometry, the beam axes of fundamental and harmonics of undulator radiation are separated with large angles over 10 µrad, which enables the selection of a specific harmonic with the help of apertures, while keeping a high photon flux. The concept of the harmonic separation was experimentally confirmed using X-ray beams from the X-ray free-electron laser SACLA.