Due to many of its attributes, Li₂B₄O₇ provides a possible material for incorporation as either a primary or companion material in future solid state neutron detectors. There is however a lack of fundamental characterization information regarding this useful material, particularly its electronic configuration. To address this, an investigation of Li₂B₄O₇(110) and Li₂B ₄O₇(100) was undertaken, utilizing photoemission and inverse photoemission spectroscopic techniques. The measured band gap depended on crystallographic direction with the band gaps ranging from 8.9±0.5 eV to 10.1±0.5 eV. The measurement yielded a density of states that qualitatively agreed with the theoretical results from model bulk band structure calculations for Li₂B₄O₇; albeit with a larger band gap than predicted, but consistent with the known deficiencies of Local Density Approximation and Density Functional Theory calculations. The occupied states of both surfaces were extremely flat; to the degree that resolving periodic dispersion of the occupied states was inconclusive, within the resolution of the system. However, both surfaces demonstrated clear periodic dispersion within the empty states very close to theoretical Brillouin zone values. These attributes also translated to a lighter charge carrier effective mass in the unoccupied states. Of the two surfaces, Li₂B₄O ₇(110) yielded the more consistent values in orthogonal directions for energy states. The presence of a bulk band gap surface state and image potential state in Li₂B₄O₇(110) was indicative of a defect-free surface. The absence of both in the more polar, more dielectric Li₂B₄O₇(100) was attributed to the presence of defects determined to be O vacancies. The results from Li₂B ₄O₇(110) were indicative of a more stable surface than Li ₂B₄O₇(100). In addition, Li 1s bulk and surface core level components were determined at the binding energies of -56.5+0.4 and -53.7+0.5 eV. Resonance features were observed along the [001] direction and were attributed to a Coster-Kronig process. Finally, the pyroelectric and piezoelectric character of Li₂B₄O ₇ was explored more deeply and a non-zero, off-axis pyroelectric coefficient for the Li₂B₄O₇ (110) direction was discovered.