Angle‐resolved photoemission from both (100) and (111) oriented, natural type IIb diamond was used to study the electronic structure of diamond. A negative electron affinity (NEA) was found on the 2×1 reconstructed diamond (100) surface. Photoemission spectra of NEA surfaces exhibit a distinctive peak due to emission from the conduction band edge. This peak was used as a reference point to correlate spectra of (100) and (111) surfaces with a NEA. A feature at ∼7.5 eV above the conduction band edge appears in the spectra of both the (111) and (100) surfaces. Angle‐resolved photoemission measurements were used to determine the energy dispersion of this feature for various off‐normal angles. The results for the surfaces were correlated, and compared to a calculated band structure. Based on this comparison we attribute this feature to emission from secondary electrons which are collected in a conduction band level at ∼7.5 eV above the conduction band edge.