A novel sequence for reversible second-order nonlinear optical (NLO) molecular switching with protonation/deprotonation has been achieved and tuned as well. The NLO switching with first hyperpolarizabilities (β0) as low as 14 × 10−30 esu (Off-phase) and as large as 1189 × 10−30 esu (On-phase) have been computed by using density functional theory (DFT). Remarkably large differences between the β0 values of benzimidazole containing chromophores and their deprotonated anions have shown their significant potential for a new type of NLO molecular switching, as (1-(4-methoxyphenyl)-2-(2-thienyl)pyrrolyl)-1,3-benzimidazole anion (1−) has a β0 value computed to be 61 × 10−30 esu, which is 4 times larger than its neutral molecule 1. This β0 value has been tuned up to 2028 × 10−30 esu by effective substitutions in the derivatives of 1− (1a−, 1b−, 1c−, and 1d−). Interestingly, the substituted compounds have illustrated robustly large off–on NLO switching with a difference in β0 values of 7, 63, 85 and 75 times larger than their neutral counterparts, respectively. TD-DFT calculations along with natural bond orbital (NBO), frontier molecular orbitals (FMOs) and molecular electrostatic potential (MEP) analyses show that the abstraction of an imido proton brings about a change in push–pull configurations resulting in a red shift for both absorption and emission spectra which subsequently leads to a high performance second-order NLO molecular switching. A similar trend of NLO switching in F− compounds of these chromophores has also been observed with significantly large β0 values having analogous electro-optical properties like deprotonated anions. Furthermore, gas-phase acidity (GPA) calculations for the neutral molecule 1 and its derivatives (1a, 1b, 1c, and 1d) have also revealed that these are rationally potent nitrogen acids and can easily be dissociated to produce stable deprotonated anions.