The all-cis 1,2,3,4,5,6-hexafluorocyclohexane C₆H₆F₆ (1) is a well-known molecule which has an unusually large molecular dipole moment (6.2 Debye), and plentiful novel excess electron compounds have been successfully designed on the basis of it recently. Inspired by 1, in this study, we tried to replace all the F atoms in molecule C₆H₆F₆ with Cl atoms and obtained the all-cis 1,2,3,4,5,6-hexachlorocyclohexane C₆H₆Cl₆ (2). By introducing alkali metal atoms and alkaline earth metal atoms, a novel series of alkalides and excess electron compounds, namely MA*⁺-2-MA⁻ (MA* = Na, K; MA = Li, Na and K) and MA*-2-MAE (MA* = Na, K; MAE = Be, Mg and Ca), were theoretically constructed and studied in this work. Our results exhibit the apparent charge transfer in MA*⁺-2-MA⁻ systems by NBO analysis. And these compounds all show good stability from the values of VIE and Gap. Especially, Na⁺-2-Li⁻ compound exhibit the largest first hyperpolarizability value (3.4 × 10⁶ au). The calculated results indicate these novel proposed species possess significantly large nonlinear optical responses. We hope this work will attract more experimental interests and efforts to design and synthesize new excellent NLO materials.