Superalkalies with low ionization potentials (IPs) can exhibit behaviors reminiscent of alkali atoms and hence be considered as potential building blocks for the assembly of novel nanostructured materials. A new series of binuclear superalkali cations M2Li2k+1+ (M = F, O, N, C) has been studied using ab initio methods. The structural features of such cations are found to be related to the central atoms. In the preferred structures of F2Li3+, O2Li5+, and N2Li7+, two central atoms are bridged by lithium atoms. While in the global minima of C2Li9+, two central carbon atoms directly link each other and the C-C unit extends to the surface of the whole system. These M2Li2k+1+ species exhibit very low vertical electron affinities of 2.74-4.61 eV at the OVGF/6-311+G(3df) level and hence should be classified as superalkali cations.