The present work gives the hydrogen dissociation energies and electronic structures of Li_8−xTi_xB₈F_yH_32−y (x, y = 0 or/and 1) compounds by first-principles density functional theory calculations, with the aim of providing new insights into the enhanced dehydrogenation of LiBH₄ with Ti or/and F additives. The results indicate that substituting more electronegative elements Ti for Li or/and F for H helps to destabilize LiBH₄, resulting in decreased hydrogen dissociation energies for favorable H-desorption. This is particularly obvious for LiBH₄ sample with Ti + F co-substitution, and associated with the decrease of Li–B, Li–H and B–H bonding interactions, the formation of Ti–B, Ti–H and Li–F bonds, as well as the presence of metallic character. Our work suggests that combined metal cation and nonmetal anion co-doping could effectively modify the properties of LiBH₄, which is useful for hydrogen storage applications.