The electronic structure and chemical bonding of β-Ta synthesized as a thin 0 0 1-oriented film (space group P4¯21m) is investigated by 4f core level and valence band X-ray photoelectron spectroscopy and compared to α-Ta bulk. For the β-phase, the 4f7/2 peak is located at 21.91 eV and with the 4f5/2 at 23.81 eV which is 0.16 eV higher compared to the corresponding 4f peaks of the α-Ta reference. We suggest that this chemical shift originates from electron screening, higher resistivity or strain in the β-Ta film. Furthermore, the 5d–5s states at the bottom of the valence band are shifted by 0.75 eV towards higher binding energy in β-Ta compared to α-Ta. This is a consequence of the lower number of nearest neighbors with four in β-Ta compared to eight in the α-Ta phase. The difference in the electronic structures, spectral line shapes of the valence band and the energy positions of the Ta 4f, 5p core-levels of β-Ta versus α-Ta are discussed in relation to calculated states of β-Ta and α-Ta. In particular, the lower number of states at the Fermi level of β-Ta (0.557 states/eV/atom) versus α-Ta (1.032 states/eV/atom) that according to Mott's law should decrease the conductivity in metals and affect the stability by charge redistribution in the valence band. This is experimentally supported from resistivity measurements of the film yielding a value of ∼170 μΩ cm in comparison to α-Ta bulk with a reported value of ∼13.1 μΩ cm.