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Hexagonal boron nitride (h-BN) has attracted considerable interest as an ultrawide bandgap (UWBG) semiconductor. Experimental studies focused on the detailed near band-edge structure of h-BN at room temperature are still lacking. We report a direct experimental measurement of the near band-edge structure performed on h-BN quasi-bulk wafers via photocurrent excitation spectroscopy (PES). PES resolved the band-to-band transitions near M- and K-points in the Brillion zone (BZ), from which the room temperature indirect band gap of EgMK∼6.02 eV, minimum direct bandgap at M-point of EgM=6.36eVand next lowest direct energy bandgap at K-point of EgK=6.56eV,have been simultaneously determined for the first time experimentally. The measured energy differences between K- and M-points in the conduction band minimum (CBM) and valence band maximum (VBM) are ΔECMK=0.54eVand ΔEVMK= 0.34 eV, respectively, in good agreement with the calculation results. Significantly differing from its III-nitride wurtzite counterparts, in which only electrons and holes in the conduction and valence band extremes at the Γ-point are predominantly involved in the optical and transport processes, the results highlighted that charge carriers associated with both M- and K-valleys control to the optical excitation, recombination and charge transport processes in h-BN.