From angle resolved photoemission, the (100) surface termination of Li2B4O7 is significantly more polar than the (110) surface termination although the accepted dipole orientation of this pyroelectric crystal is along (001). Consistent with the surface termination, the surface charging at the surface of (100) is significantly greater than observed at (110) and plays a role in the surface photovoltage effects. Because of the different interfaces formed, device properties likely depend upon crystal faces of lithium borate.