The electronic structures of the highest occupied molecular orbital (HOMO) or the HOMO-derived valence bands dominate the transport nature of positive charge carriers (holes) in organic semiconductors. In the present study, the valence-band structures of single-crystal pentacene and the temperature dependence of their energy-momentum dispersion relations are successfully demonstrated using angle-resolved ultraviolet photoelectron spectroscopy (ARUPS). For the shallowest valence band, the intermolecular transfer integral and effective mass of the holes are evaluated as 43.1 meV and 3.43 times the electron rest mass, respectively, at room temperature along the crystallographic direction for which the widest energy dispersion is expected. The temperature dependence of the ARUPS results reveals that the transfer integral values (hole effective mass) are enhanced (reduced) by ∼20% on cooling the sample to 110 K.