We present a MIDIX basis set for Li that accurately predicts geometries, charge distributions, and partial atomic charges for a test set of compounds at a reasonable cost. MIDIX basis sets, which are also called MIDI!, are heteroatom-polarized split-valence basis sets in which the polarization functions are optimized in order to predict realistic molecular geometries and atomic partial charges. The MIDIX basis set uses the core, inner valence, and outer valence basis functions of the MIDI basis set plus an additional Gaussian basis function. We optimized the p exponent to obtain realistic predictions of geometry, density dipole moments, and Löwdin dipole moments at the Hartree-Fock and hybrid density functional levels of theory, using the mPW1PW91 hybrid density functional for the latter. The MIDIX basis set predicts Hartree-Fock geometries and Hartree-Fock and hybrid density functional Löwdin dipole moments more accurately than either the 3-21G(d) or 6-31G(d) basis set for most of the compounds in our training set. It also predicts more accurate Hartree-Fock and hybrid density functional density dipole moments than the 3-21G(d) basis set. The present results show that the basis set is expected to be very useful for calculating geometries and electrostatic properties of lithium compounds containing H, C, N, O, F, Si, P, S, Cl, Br, and I, especially organolithium and lithium-sulfur compounds.