High-resolution angle resolved ultraviolet photoelectron spectroscopy measurements were conducted on rubrene single crystals successfully through relief of the sample charging assisted by a laser illumination. Significant dispersion of the valence band was clearly resolved. The band width W and the hole effective mass m
h* were estimated to be 0.4 eV and 0.7m0, respectively, along the most conductive direction. The present results strongly suggest that the transport nature in rubrene single crystals should be described in the band transport framework of a delocalized charge carrier.