Ionic liquids composed of dicyanamide anion and various imidazolium-based cations were prepared, and the influence of structural variations such as substituting a hydrogen at 2-position and changing the sort of alkyl group at 1-position of imidazolium cations on their thermal behavior, density, solvatochromic effects, viscosity, ionic conductivity, and surface tension was characterized. The substitution of the 2-hydrogen for methyl group or N-methylimidazole decreases the fluidity and ionic conductivity, mainly caused by the increased cohesive energy associated with the increasing cation size. Chain branching at 1-position also gives rise to the pronounced depression of the fluidity and ionic conductivity, presumably as a consequence of the increased pi-pi interactions between imidazolium rings. We found that the surface tension of the present ionic liquids is in inverse proportion to the molar concentration, which can be originally rationalized on the basis of the hole theory.