This work concentrates on the development of eutectic PCMs (ePCMs) that can effectively store and release thermal energy, showcasing high melting enthalpies, stability under thermal cycling, and lower flammability than pure diols. The first part presents the synthesis and characterization of dicationic ionic liquids (ILs), followed by the (solid + liquid) phase equilibrium, 1) + 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, or 1,12-dodecanediol (2)} systems. Eight ePCMs with enthalpies of melting varying from (190.1 to 204.5) J g −1 were determined. In the proposed systems, the bromide anion of the IL is the donor, and the hydroxyl group in the diol is the acceptor of the electron pair. The thermophysical characterization of pure ILs and the eutectic mixtures, including melting point, latent heat, as well as temperature and enthalpy of (solid + solid) phase transition, were determined by DSC analysis. Additionally, the composite systems of [(i-Quin) 2 C 6 ][2Br] and [(i-Quin) 2 C 10 ][2Br] with 1,8-octanediol and additions of single-walled carbon nanotubes (SWCNTs) and expanded graphite (EG) were prepared and characterized in terms of stability and performance. The research offers insights into the potential of these ePCMs in thermal energy storage applications, emphasizing their high latent heat and efficient thermal conductivity, especially when combined with carbon materials such as EG.