We present a first-principles study of the formation and migration of native defects in lithium hydride (LiH), a material of interest in hydrogen storage and lithium-ion batteries. We find that the negatively charged lithium vacancy and positively charged hydrogen vacancy are the dominant defects in LiH with a formation energy of about 0.85 eV. With this low energy, LiH can be a good provider of Li+ and/or H- ions. Based on our results, we discuss the role of LiH in its reactions with another reactant which are important in hydrogen storage and lithium-ion batteries, and explain the ionic conductivity and hydrogen surface loss as observed in experiments. (C) 2013 Elsevier B.V. All rights reserved.