A theoretical study was performed using Density Functional Theory (DFT) to investigate the impact of π-conjugated aliphatic chain growth on the chemical and electronic properties of hybrid antimony pentachloride salts with pyridine- and imidazolium-based cations. Ten molecular systems were optimized to determine their ground-state geometry. Using conceptual DFT, parameters such as chemical hardness, electrophilicity index, electroaccepting power, and electrodonating power were studied. The energy gap was obtained for all ten molecular systems, ranging from −4.038 to −3.706 eV as the chain length increased, favoring intramolecular charge transfer in long-chain systems. Natural bond orbital (NBO) analysis showed charge redistribution between anion and cation as the π-conjugated aliphatic chain grows. At the same time, non-covalent interaction (NCI) studies revealed key attractions and repulsive interactions, such as H···Cl and Cl···π, which are modulated by chain length. These results demonstrate that the structural modification of the cation allows for the fine-tuning of the electronic properties of ionic liquids (ILs). Increasing the conjugated aliphatic chain length was observed to reduce the chemical hardness and electrophilicity index, as well as affecting the Egap of the molecular systems. This work demonstrates that there is an optimal size for the inorganic ion, allowing it to form an optimal IL compound.