<p>In this work motivated by the excellent electron transfer properties of azulenequinones (AZQs) in biological systems, and as a first attempt, we explore how two-parent azulenequinones (abbreviated as 1,5AZQ and 1,7AZQ) and their derivatives (substituted at 3 positions with halogens (F, Cl, and Br) and NMe₂ and MO) can define their behavior in Li-ion batteries (LIBs). Through DFT-B3LYP/6–311 + G(d,p) calculations, the electrochemical properties of 12 isolated AZQs and their 36 lithiated AZQs were examined. The maximum accepted number of electrons was determined from the vertical electron affinity considering the solvation effect in 1,2-dimethoxymethane, which&#xa0;suggested that isolated AZQs predominately undergo one-electron redox reactions, the two-electron redox reaction could take place while the three-electron redox reactions are not expected to occur. The electronic conductivity of AZQs as cathode materials has been finely tuned by changing the positions of carbonyl groups and introducing different substituents. The calculated binding energies of the lithiated AZQs are negative, indicating a favorable binding process, and the carbonyl oxygen forms a chemical bond with a Li atom. Redox potentials of all lithiated configurations of the parent AZQs and those substituted with halogen atoms are significantly larger than those substituted with NMe₂ and MO. As part of the study, the effect of another solvent (acetonitrile) on the parameters calculated was investigated. According to our findings, both the location of redox- active sites, the nature of substitutes (different electronegativity and electron-donating power), and the solvent are important factors in tuning organic rechargeable batteries.</p>