In this study, the structures and field-emission properties of Li-decorated buckled α-borophene (BBP) were investigated by first-principles density functional theory at the PW91 level. Using the computed binding energies, Hirshfeld- and electrostatic potential-derived charges, induced dipole moments, densities of states, and ionization potentials, we evaluated the influence of an applied electric field on the structural stability, work function, and field-emission current of the Li-decorated BBP nanostructures. Furthermore, we also explored the quantitative dependence of the emission current on the electric field, Li concentration, and molecular orbitals. The computed results indicated that increasing the electric field and Li concentration has a considerably positive effect on the field-emission performance of the Li-decorated BBPs. Besides advantages including small work functions and low ionization potentials, most remarkably, the field-emission current can be as high as 48.81 μA in Li4/BBP (supercell with 36 atoms only) under a rather small applied electric field of 0.05 V Å-1, which rivals the highest value of the graphene-BN nanocomposite among all the theoretical nanostructures presented to date. Our results highly support the fact that Li-decorated BBPs can be appealing field-emission cathode materials with an extremely high emission current.