<p>New potassium imidazolate [K⁺][IMI⁻] and lithium imidazolate [Li⁺][IMI⁻] hybrid organic–inorganic salt frameworks were synthesized and characterized using Fourier-transform infrared (FTIR),¹H-nuclear magnetic resonance (NMR),¹³C-NMR, x-ray diffraction, and differential scanning calorimetry (DSC) thermal analysis. The conductivity of imidazole liquid doped with lithium ions is strongly influenced by frequency and temperature. At higher frequencies, ions have less time to respond to the electric field, resulting in reduced temperature sensitivity. Ion migration becomes more challenging at higher frequencies, as indicated by the increase in activation energy with frequency. These results apply to electrochemical systems where temperature and frequency significantly affect material performance, such as batteries, capacitors, and ionic sensors. HF, MP2, and density functional theory (DFT) calculations using several quantum exchange-correlation functionals, including B3LYP, PBE0, CAM-B3LYP, and <i>ω</i>B97X-D, have been carried out in detail to investigate the nonlinear optical properties. The results indicate that these imidazolate-based hybrid organic–inorganic salts are promising candidates for optical and optoelectronic devices.</p>