||To enhance the thermal stability of ionic liquids (ILs) and increase the latent heat, the effect of amount of hydrogen bonds for geminal dicationic ionic liquids (DILs) was investigated and compared to that of monocationic analogues. A series of geminal dicationic ionic liquids with alkyl chain or electronegativity functional groups in the imidazolium were synthesized. Thermal stability was determined by TGA; melting point, heat of fusion, and heat capacity were investigated by DSC for synthetic DILs. The effect of molecular structure on the heat of fusion was examined by changes alkyl side-chain, linkage chain, C2-H of imidazole ring, and functional groups. Hydrogen bonding in DILs was studied, in the case of C-2(eim)(2)(Br)(2), by single-crystal X-ray diffraction. The thermal analysis results indicate that functionalized geminal dicationic ionic liquids show excellent thermal stability. The decomposition temperatures of geminal dicationic ionic liquids can be up to 603.74 K, and the latent heat can reach 159.35 J g(-1). It is increased on average by 64.5% and 212.5%, respectively, as compared to alkyl chain ionic liquid (C(4)mim)Br. It can be expected that these geminal dicationic ionic liquids are suitable for thermal storage applications.