The ground states of the isovalent molecules NLi2 ((X) over tilde(2)II(u)) and PLi2 ((X) over tilde(2)B(1)), along with some low-lying excited states (B-2(2),(4) Sigma(g)(-), (2) Sigma(g)(-), (4) Sigma(u)(-), (2) Sigma(u)(-), and (2)A(1)), have been examined using ab initio CISD, CASSCF, and MRCI methods in conjunction with relatively large correlation consistent basis sets. We report total energies, geometries, binding energies, Mulliken charges, energy gaps, and for certain states, potential energy curves. All states examined are bound with respect to the ground-state atoms N or P(S-4) + 2Li(S-2), while the mean binding energies N-Li and P-Li of NLi2 and PLi2 are 42.5 and 40.2 kcal/mol, respectively.